Weatherable, thermostable polymers having improved flow composition

ABSTRACT

A copolymer composition comprises an arylate polyester unit, an aromatic carbonate unit, and a soft-block moiety, wherein individual occurrences of the soft block moiety are linked by a spacer unit comprising one or more of the arylate polyester units, one or more of the aromatic carbonate units, or a combination comprising each of these. In one embodiment, a soft block moiety comprises a polysiloxane unit. A film of the composition has a percent transmittance of greater than or equal to 60% as determined according to ASTM D1003-00. A method of forming a copolymer composition is disclosed, comprising substantially forming the bis-haloformates of a dihydroxy compound comprising an arylate polyester unit, and a dihydroxy compound comprising a soft-block moiety, and reacting the bis haloformates with a dihydroxy aromatic compound.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.10/307,873, filed Dec. 2, 2002, now U.S. Pat. No. 6,861,482, issued Mar.1, 2005, which is a continuation-in-part of U.S. Pat. No. 6,610,409,issued Aug. 26, 2003, which is a continuation-in-part of U.S. Pat. No.6,306,507, issued Oct. 23, 2001, which claims the benefit of U.S.Provisional Application No. 60/134,692, filed May 18, 1999, and whichapplications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to polymers that are thermostable,weatherable and have good flow characteristics and good ductilitycharacterisitics especially at lower temperatures. More particularly,the present invention relates to poly(resorcinolphthalate-polycarbonate) copolymers that include soft-block moieties.Such polymers may be advantageously used in multilayer articles asUV-protective coatings or as weatherable, thermoformable articles withgood ductility.

Various polymeric articles have a problem of long-term colorinstability. In many cases this instability is seen as yellowing of thepolymer or loss of glossiness. Yellowing of polymers is often caused bythe action of ultraviolet radiation. Such yellowing is frequentlydesignated “photoyellowing”. To reduce photoyellowing, ultravioletabsorbing compounds (UVA's) may be incorporated into the polymer. Forthe most part, UVA's are low molecular weight compounds, which must beemployed at relatively low levels, typically up to 1% by weight, toavoid degradation of the physical properties of the polymer. Forexample, incorporation of UVAs may lead to loss of impact strength, lossof high temperature properties as reflected in heat distortiontemperature, and/or susceptibility to attack by organic liquids.

Polymers comprising polyesters containing resorcinol arylate chainmembers often provide good resistance to photoyellowing and loss ofgloss, and thus are considered to possess good “weatherability.” Thearylate moieties typically contain isophthalate, terephthalate, andmixtures of isophthalate and terephthalate. Polyesters of resorcinolarylates may provide good protection against photoyellowing when coatedover a resinous substrate.

The good weatherability properties of polyesters containing resorcinolarylate units is believed to arise in large part from the screeningeffect these polymers may provide against ultraviolet (UV) light. Onexposure to UV light, polymers comprising resorcinol arylate chainmembers can undergo a photochemically-induced Fries rearrangement thatconverts at least a portion of the polymer from polyester chain membersto o-hydroxybenzophenone-type chain members. Theo-hydroxybenzophenone-type chain members act to screen against furtherUV exposure and protect UV-sensitive components underlying a resorcinolarylate-containing composition.

Polyesters containing resorcinol arylate chain members may be made usingmelt polymerization or interfacial methods. Polyesters containingresorcinol arylate chain members may be prepared by melt methods asdisclosed in U.S. Pat. No. 4,127,560 and in Japanese Kokai 1/201,326.The methods, however, do not allow the incorporation of greater than 30mole percent terephthalate and were found to result in a polyesterhaving unacceptable levels of color. Polyesters containing resorcinolarylate chain members have also been prepared by an interfacial method(see e.g., U.S. Pat. No. 3,460,961; and Eareckson, Journal of PolymerScience, vol. XL, pp. 399–406 (1959)).

One common problem in the preparation of resorcinol arylate-containingpolyesters is the presence of destabilizing anhydride bonds, which arebelieved to be easily broken under thermal conditions typical ofpolycarbonate processing to produce shorter chains terminated by acidend groups. These acid end-groups may in turn, accelerate the hydrolysisof the arylate moiety, generating additional carboxyl and hydroxylend-groups, and further contributing to molecular weight degradation andloss of other desirable properties. Methods for preparing thermostableresorcinol arylate-containing polyesters substantially free of anhydridebonds are described in commonly owned U.S. Pat. Nos. 6,265,522,6,291,589, 6,294,647, and 6,306,507.

The good weatherability properties of polymers comprising resorcinolarylate chain members make them especially useful in blends and inmultilayer articles in which the polymers act as a protecting layer formore sensitive substrate components. Multilayer articles containinglayers made from resorcinol arylate-containing polyester have beendescribed by Cohen et al., Journal of Polymer Science: Part A-1, vol. 9,3263–3299 (1971) and in U.S. Pat. No. 3,460,961. However, the coatingsdeveloped using this method were thermally unstable and had to beapplied by solution coating followed by evaporation of the solvent.Also, Japanese Kokai 1/199,841 discloses a method for coating bottlesusing a polyester of resorcinol and isophthalic acid. The method waslimited, however, in only describing coating of poly(ethyleneterephthalate) substrates.

Thus, polymers comprising resorcinol arylate have proven to be veryuseful materials for weatherable applications, and methods are availablefor making polymers comprising resorcinol arylate that are bothweatherable and, due to the almost complete elimination of anhydridelinkages, thermostable. Additionally, this family of polymers also hasgood solvent resistance, good scratch resistance, and excellentductility. One limitation of this family, however, is the fact that themelt viscosity is higher than polycarbonates with comparable molecularweights. This limitation can potentially preclude some applications,such as use of the polymer for coating UV-sensitive articles. Also, forinjection molding of blends with other polymers or the manufacture ofmultilayer films made by co-extrusion, a match of melt viscosity ispreferred. In addition, manufacture of large or thin-walled partsrequires low melt viscosity. Hoover and Sybert (U.S. Pat. No. 5,932,677)disclose polymers with a low melt viscosity, prepared in a one-stepprocess by reacting together a siloxane, a bisphenol and an aromaticdicarboxylic acid halide. However, the method results in polymers thatare opaque, and thus may be of limited use where a clear coating iscalled for.

Hoover and Sybert (U.S. Pat. No. 5,455,310) also disclose polysiloxanepolycarbonate block copolymers further comprising phenolphthaleinpolyester blocks with improved ductility, especially at lowtemperatures.

What is needed then, is a way to produce transparent, thermostable,weatherable polymers comprising resorcinol arylate with good flowcharacteristics at the temperatures used for extrusion (sheet, film, andinjection molding), and improved ductility, especially at lowtemperatures. To be cost effective, the method should employ componentsthat are easily obtained and that can be incorporated into existingpolymerization protocols.

BRIEF SUMMARY OF THE INVENTION

A copolymer composition comprises an arylate polyester unit, an aromaticcarbonate unit, and a soft-block moiety, wherein individual occurrencesof the soft block moiety are substantially linked by a spacer unitcomprising one or more of the arylate polyester units, one or more ofthe aromatic carbonate units, or a combination comprising each of these.In one embodiment, the soft block moiety comprises a polysiloxane unit.A film of the copolymer composition has a percent transmittance ofgreater than or equal to 60% as determined according to ASTM D1003-00.

In another aspect, a method of forming a copolymer composition comprisessubstantially forming the bis-haloformates of a dihydroxy compoundcomprising an arylate polyester unit, and a dihydroxy compoundcomprising a soft-block moiety, and reacting the bis-haloformates with adihydroxy aromatic compound.

DETAILED DESCRIPTION

The present invention may be understood more readily by reference to thefollowing detailed description of preferred embodiments of the inventionand the examples included herein. In the specification and the claimswhich follow, reference will be made to a number of terms which shall bedefined to have the following meanings:

The singular forms “a”, “an” and “the” include plural references unlessthe context clearly dictates otherwise.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where the event occurs and instances where it does not.

The terms “first,” “second,” “first part,” “second part,” and the like,where used herein, do not denote any order, quantity, or importance, andare used to distinguish one element from another, unless specificallystated otherwise.

As used herein the term “polycarbonate” refers to polycarbonatesincorporating structural units derived from one or more dihydroxyaromatic compounds and includes copolycarbonates andpolyestercarbonates.

“BPA” is herein defined as bisphenol A or2,2-bis(4-hydroxyphenyl)propane.

“Catalytically effective amount” refers to the amount of the catalyst atwhich catalytic performance is exhibited.

As used herein the term “monofunctional phenol” means a phenolcomprising a single reactive hydroxy group.

As used herein the term “aliphatic radical” refers to a radical having avalence of at least one comprising a linear or branched array of atomswhich is not cyclic, optionally substituted with substituents selectedfrom the group consisting of lower alkyl, lower alkoxy, loweralkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, aminooptionally substituted by alkyl, carboxy, carbamoyl optionallysubstituted by alkyl, aminosulfonyl optionally substituted by alkyl,silyloxy optionally substituted by alkoxy, alkyl, or aryl, silyloptionally substituted by alkoxy, alkyl, or aryl, nitro, cyano, halogen,or lower perfluoroalkyl, multiple degrees of substitution being allowed.Thus, the array may include heteroatoms such as nitrogen, sulfur andoxygen or may be composed exclusively of carbon and hydrogen. Examplesof aliphatic radicals include methyl, methylene, ethyl, ethylene, hexyl,hexamethylene and the like.

As used herein the term “aromatic radical” refers to a radical having avalence of at least one comprising at least one aromatic groupoptionally substituted with substituents selected from the groupconsisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, loweralkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy, mercapto, aminooptionally substituted by alkyl, carboxy, carbamoyl optionallysubstituted by alkyl, aminosulfonyl optionally substituted by alkyl,silyloxy optionally substituted by alkoxy, alkyl, or aryl, silyloptionally substituted by alkoxy, alkyl, or aryl, nitro, cyano, halogen,or lower perfluoroalkyl, multiple degrees of substitution being allowed.Examples of aromatic radicals include phenyl, pyridyl, furanyl, thienyl,naphthyl, phenylene, and biphenyl. The term includes groups containingboth aromatic and aliphatic components, for example a benzyl group.

As used herein the term “cycloaliphatic radical” refers to a radicalhaving a valence of at least one comprising an array of atoms which iscyclic but which is not aromatic optionally substituted withsubstituents selected from the group consisting of lower alkyl, loweralkoxy, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy,mercapto, amino optionally substituted by alkyl, carboxy, carbamoyloptionally substituted by alkyl, aminosulfonyl optionally substituted byalkyl, silyloxy optionally substituted by alkoxy, alkyl, or aryl, silyloptionally substituted by alkoxy, alkyl, or aryl, nitro, cyano, halogen,or lower perfluoroalkyl, multiple degrees of substitution being allowed.The array may include heteroatoms such as nitrogen, sulfur and oxygen ormay be composed exclusively of carbon and hydrogen. Examples ofcycloaliphatic radicals include cyclopropyl, cyclopentyl cyclohexyl,tetrahydrofuranyl and the like.

As used herein, the term “alkyl” refers to a straight or branched chainhydrocarbon having from one to ten carbon atoms, optionally substitutedwith substituents selected from the group consisting of lower alkyl,lower alkoxy, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy,mercapto, amino optionally substituted by alkyl, carboxy, carbamoyloptionally substituted by alkyl, aminosulfonyl optionally substituted byalkyl, silyloxy optionally substituted by alkoxy, alkyl, or aryl, silyloptionally substituted by alkoxy, alkyl, or aryl, nitro, cyano, halogen,or lower perfluoroalkyl, multiple degrees of substitution being allowed.Examples of “alkyl” as used herein include, but are not limited to,methyl, n-butyl, n-pentyl, isobutyl, and isopropyl, and the like. Asused herein, the term “lower” refers to a group having between one andsix carbons.

As used herein, the term “alkylene” refers to a straight or branchedchain divalent hydrocarbon radical having from one to ten carbon atoms,optionally substituted with substituents selected from the groupconsisting of lower alkyl, lower alkoxy, lower alkylsulfenyl, loweralkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted byalkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyloptionally substituted by alkyl, silyloxy optionally substituted byalkoxy, alkyl, or aryl, silyl optionally substituted by alkoxy, alkyl,or aryl, nitro, cyano, halogen, or lower perfluoroalkyl, multipledegrees of substitution being allowed. Examples of “alkylene” as usedherein include, but are not limited to, methylene, ethylene, and thelike.

As used herein, the term “alkenyl” refers to a hydrocarbon radicalhaving from two to ten carbons and at least one carbon-carbon doublebond, optionally substituted with substituents selected from the groupconsisting of lower alkyl, lower alkoxy, lower alkylsulfenyl, loweralkylsulfonyl, oxo, hydroxy, mercapto, amino optionally substituted byalkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyloptionally substituted by alkyl, silyloxy optionally substituted byalkoxy, alkyl, or aryl, silyl optionally substituted by alkoxy, alkyl,or aryl, nitro, cyano, halogen, or lower perfluoroalkyl, multipledegrees of substitution being allowed.

As used herein, the term “alkenylene” refers to a straight or branchedchain divalent hydrocarbon radical having from two to ten carbon atomsand one or more carbon—carbon double bonds, optionally substituted withsubstituents selected from the group consisting of lower alkyl, loweralkoxy, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy,mercapto, amino optionally substituted by alkyl, carboxy, carbamoyloptionally substituted by alkyl, aminosulfonyl optionally substituted byalkyl, silyloxy optionally substituted by alkoxy, alkyl, or aryl, silyloptionally substituted by alkoxy, alkyl, or aryl, nitro, cyano, halogen,or lower perfluoroalkyl, multiple degrees of substitution being allowed.Examples of “alkenylene” as used herein include, but are not limited to,ethene-1,2-diyl, propene-1,3-diyl, methylene-1,1-diyl, and the like.

As used herein, the term “hydrocarbyl” refers to a substituted orunsubstited monovalent group comprising carbon and hydrogen, and may bealiphatic, aromatic, or a combination of aliphatic and aromatic. Ahydrocarbyl group may also include one or more heteroatoms, such asoxygen, nitrogen, sulfur, and the like, wherein the heteroatom may bepresent as a substituent, e.g., a heteroatom-containing group such ashalo, oxo, heterocycle, alkoxy, hydroxy, aryloxy, —NO₂, carboxy, acyl,amino, alkylamino, amido, and the like, as long as the substituent doesnot substantially interfere with manufacture or use of the compositions.The heteroatom may also be present as essential structural component ofthe group, for example in the form of an ester or ether linkage, as longas the heteratom does not substantially interfere with manufacture oruse of the compositions. A hydrocarbyl group may be linear, branched, orcyclic, including polycyclic, or a combination comprising one or more ofthese. Similarly, the term “hydrocarbylene,” as used herein, refers to adivalent hydrocarbyl group. Apart from the specified valences and anylimitations implied by a specified number of atoms comprising thesegroups, no other specific structure is implied.

As used herein, “cycloalkyl” refers to an alicyclic hydrocarbon groupwith one or more degrees of unsaturation, having from three to twelvecarbon atoms, optionally substituted with substituents selected from thegroup consisting of lower alkyl, lower alkoxy, lower alkylsulfenyl,lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionallysubstituted by alkyl, carboxy, carbamoyl optionally substituted byalkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano,halogen, or lower perfluoroalkyl, multiple degrees of substitution beingallowed. “Cycloalkyl” includes by way of example cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, and thelike.

As used herein, the term “cycloalkylene” refers to a non-aromaticalicyclic divalent hydrocarbon radical having from three to twelvecarbon atoms and optionally possessing one or more degrees ofunsaturation, optionally substituted with substituents selected from thegroup consisting of lower alkyl, lower alkoxy, lower alkylsulfenyl,lower alkylsulfonyl, oxo, hydroxy, mercapto, amino optionallysubstituted by alkyl, carboxy, carbamoyl optionally substituted byalkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano,halogen, or lower perfluoroalkyl, multiple degrees of substitution beingallowed. Examples of “cycloalkylene” as used herein include, but are notlimited to, cyclopropyl-1,1-diyl, cyclopropyl-1,2-diyl,cyclobutyl-1,2-diyl, cyclopentyl-1,3-diyl, cyclohexyl-1,4-diyl,cycloheptyl-1,4-diyl, or cyclooctyl-1,5-diyl, and the like.

As used herein, the term “aryl” refers to a benzene ring or to anoptionally substituted benzene ring system fused to one or moreoptionally substituted benzene rings, optionally substituted withsubstituents selected from the group consisting of lower alkyl, loweralkoxy, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy,mercapto, amino optionally substituted by alkyl, carboxy, tetrazolyl,carbamoyl optionally substituted by alkyl, aminosulfonyl optionallysubstituted by alkyl, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy,heteroaroyloxy, alkoxycarbonyl, silyloxy optionally substituted byalkoxy, alkyl, or aryl, silyl optionally substituted by alkoxy, alkyl,or aryl, nitro, cyano, halogen, or lower perfluoroalkyl, multipledegrees of substitution being allowed. Examples of aryl include, but arenot limited to, phenyl, 2-naphthyl, 1-naphthyl, 1-anthracenyl, and thelike.

As used herein, the term “arylene” refers to a benzene ring diradical orto a benzene ring system diradical fused to one or more optionallysubstituted benzene rings, optionally substituted with substituentsselected from the group consisting of lower alkyl, lower alkoxy, loweralkylsulfanyl, lower alkylsulfenyl, lower alkylsulfonyl, oxo, hydroxy,mercapto, amino optionally substituted by alkyl, carboxy, tetrazolyl,carbamoyl optionally substituted by alkyl, aminosulfonyl optionallysubstituted by alkyl, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy,heteroaroyloxy, alkoxycarbonyl, silyloxy optionally substituted byalkoxy, alkyl, or aryl, silyl optionally substituted by alkoxy, alkyl,or aryl, nitro, cyano, halogen, or lower perfluoroalkyl, multipledegrees of substitution being allowed. Examples of “arylene” include,but are not limited to, benzene-1,4-diyl, naphthalene-1,8-diyl, and thelike.

As used herein, the term “direct bond”, where part of a structuralvariable specification, refers to the direct joining of the substituentsflanking (preceding and succeeding) the variable taken as a “directbond”.

The present invention describes polymers that are thermostable,weatherable and have good flow characteristics. The present inventionprovides various methods to produce resorcinol arylate polycarbonatecopolymers that include soft-block moieties. In addition to beingthermostable to conditions typically required for polymer processing andproviding good protection against UV degradation, such polymers havegood scratch resistance, good solvent resistance, and excellentductility. Such polymers may be used in multilayer articles asUV-protective coatings or for flow injection applications.

Thus, in one aspect, the present invention describes a resorcinol esterpolycarbonate polymer having good flow characteristics comprising: (a) aresorcinol arylate polyester chain; (b) at least one organic carbonategroup; and (c) at least one soft-block chemical moiety.

In an embodiment, the polymer is made using an interfacial method. In anembodiment, the resorcinol arylate polyester chain comprises thecondensation of at least one resorcinol moiety with at least onedicarboxylic acid dichloride, wherein the dicarboxylic acid residuescomprise a monocyclic aromatic moiety or a polycyclic aromatic moiety.

Preferably, the resorcinol arylate polyester chain is substantially freeof anhydride linkages. More preferably, and to generate a chainsubstantially free of anhydride linkages, the resorcinol arylatepolyester chain comprises the condensation of at least one resorcinolmoiety with at least one dicarboxylic acid dichloride while maintainingthe pH between 3 and 8.5 through the presence of an acid acceptor,wherein the total molar amount of acid chloride groups isstoichiometrically deficient relative to the total molar amount ofphenolic groups on the resorcinol moiety.

In an embodiment, the resorcinol moiety used to generate the resorcinolarylate polyester chain comprises compounds of Formula I

wherein R^(y) is at least one of C₁₋₁₂ alkyl or halogen, and n is 0–3.

Preferably, the resorcinol moiety used to generate the resorcinolarylate polyester chain comprises unsubstituted resorcinol, 2-methylresorcinol, and mixtures thereof.

In an embodiment, the dicarboxylic acid residues comprise a monocyclicaromatic moiety or a polycyclic aromatic moiety. Preferably, the atleast one dicarboxylic acid dichloride comprises isophthaloyldichloride, terephthaloyl dichloride, naphthalene-2,6-dicarboxylic aciddichloride and mixtures thereof.

In an embodiment, the resorcinol ester polycarbonate polymer comprises abackbone structure as illustrated in Formula IV:

where R^(y) is at least one of C₁₋₁₂ alkyl or halogen, n is 0–3, m is atleast about 8, p is at least about 10, and R^(x) is at least onedivalent organic radical, where for the purposes of Formula IV, theorganic radical comprises an aromatic, aliphatic, or cycloaliphaticradical. More specifically, an aliphatic or cycloaliphatic divalentorganic radical R^(x) may comprise C₁–C₃₀ alkyl, C₄–C₃₀ cycloalkyl, orC₆–C₃₀ aryl, C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy or C₆–C₃₀ aryloxy

It will be appreciated that a divalent organic radical R^(x) may derivefrom its dihydroxy compound HO—R^(x)—OH. Suitable aliphatic orcycloaliphatic diols include, but are not limited to, ethylene glycol,propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,11-undecanediol, 1,12-dodecanediol, 2,2-dimethyl-1,3-propanediol,diethyleneglycol, dipropyleneglycol, polyethylene glycols, polypropyleneglycols, poly-(ethylene-propylene) glycols, cyclohexane diol,1,4-dihydroxymethyl cyclohexane, methylene-bis-cyclohexanol,isopropylidine-bis-cyclohexanol, 1,4 dihydroxydecalin,1,5-dihydroxydecalin, 2,6-dihydroxydecalin, and the like. A combinationof one or more of the foregoing may be used.

Preferably, R^(x) comprises a divalent organic radical derived from abisphenol of Formula VIII

wherein R³–R¹⁰ are independently a hydrogen atom, halogen atom, nitrogroup, cyano group, C₁–C₃₀ alkyl group, C₄–C₃₀ cycloalkyl group, orC₆–C₃₀ aryl group, a C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy or C₆–C₃₀aryloxy; W is a direct bond, or an oxygen atom, sulfur atom, a C═Ogroup, a SO₂ group, C₁–C₂₀ aliphatic radical, C₆–C₂₀ aromatic radical,C₆–C₂₀ cycloaliphatic radical or the group,

wherein R¹¹ and R¹² are independently a hydrogen atom, C₁–C₂₀ alkylgroup, C₄–C₂₀ cycloalkyl group, or C₄–C₂₀ aryl group; or R¹¹ and R¹²together form a C₄–C₂₀ cycloaliphatic ring which is optionallysubstituted by one or more C₁–C₂₀ alkyl, C₆–C₂₀ aryl, C₅–C₂₁ arylalkyl,C₅–C₂₀ cycloalkyl groups or a combination thereof. In an embodiment, thedihydroxy aromatic compounds comprise alkyl or alkylene esters.

The term soft-block as used herein, indicates that some segments of thepolymers are made from non-aromatic monomer units. Such non-aromaticmonomer units are generally aliphatic and are known to impartflexibility to the soft-block-containing polymers. The copolymersinclude those comprising structural units of Formulas IX, X, XI, XII,XIII, XIV and XVI, as described herein.

In an embodiment, the soft-block moiety comprises structural units ofFormulas IX, X, or XI:

wherein R^(y) is at least one of C₁₋₁₂ alkyl or halogen, and n is 0–3; Zis a divalent aliphatic radical, or a C₃₋₂₀ straight chain alkylene suchas (CH₂)₂₀; and s is 0–10, R¹³ is a C₃₋₂₀ straight chain alkylene, aC₃₋₁₀ branched alkylene, a C₄₋₁₀ cyclo- or bicycloalkylene group,CH₂(CH₂OCH₂)_(r)CH₂, where r is 1–20, or a polyester comprising theformula CH₂([CH2]_(b)O[CH2]_(b))_(c)CH₂, where b is 1–3 and c is 1–10;and R¹⁴ and R¹⁵ each independently represent

In Formulas IX, X and XI, as elsewhere herein, wavy lines representpolymer chain structure.

In an embodiment, the soft-block moiety comprises an aliphatic ester. Inan embodiment, the aliphatic ester comprises at least six carbons. Morepreferably, the aliphatic ester comprises at least eight carbons, andeven more preferably, the aliphatic ester comprises at least tencarbons. Preferably, the aliphatic ester is introduced into the polymerby co-reaction of an aliphatic diacid or diacid chloride with anisophthaloyl or terephthaloyl chloride for polymerization with theresorcinol monomer units. More preferably, the soft-block moietycomprises carboxy-terminated polybutadiene, carboxy-terminatedbutadiene-acrylonitrile copolymer, adipoyl chloride, sebacoyl chloride,or dodecanoyl chloride.

In an embodiment, the soft-block moiety comprises at least one hydroxyend-group. Preferably, the hydroxy terminated soft-block moiety issubstituted for a portion of the resorcinol moiety used to produce theresorcinol arylate chain.

In an embodiment, the soft-block moiety comprises oligomers ofdiethylene glycol, tetraethylene glycol, or low molecular weightpolyethylene glycol. Preferably, the molecular weight of thepolyethylene glycol is less than 600 Mw.

In another embodiment, the soft-block moiety comprises ahydroxy-terminated aliphatic polyester or polycarbonate oligomer.Preferably, the hydroxy-terminated aliphatic polyester or polycarbonateoligomer is substituted for a portion of the resorcinol to react withthe dicarboxylic acid dichloride during synthesis of the polymer.

In yet another embodiment, the soft-block moiety comprisespoly(tetrahydrofuran) diol or alternatively, an o,p-mixture ofcitronellyl citronellate diphenol (CCDP). Preferably, thepoly(tetrahydrofuran) diol or CCDP reacts with the dicarboxylic aciddichloride for incorporation into the polymer.

The present invention also provides for heterofunctional soft-blockmoieties. Thus, in another embodiment, the soft-block moiety comprises aresidue derived from a siloxane oligomer as shown in Formula XII,

wherein q is in one embodiment 1–99, and in another embodiment 30–70,specifically 20–60. In one particular embodiment q has a value of 1–20.In another particular embodiment q has a value of 10–20.

In an embodiment, the siloxane oligomer in Formula XII may range fromone to at least twenty siloxane units. Thus, the siloxane oligomer maycomprise α,ω(3-(4-hydroxy-3-methoxy)-propyl)-deca(dimethylsiloxane)(ED10E), 1,3(bis-3-(4-hydroxy-3-methoxy)-propyl)-1,1,3,3,-tetramethyldisiloxane (EMME), or oligomers of similar structure.

In another embodiment heterofunctional soft-block moieties may comprisea residue derived from a siloxane oligomer as shown in Formula XVI,

wherein the moiety Ar is derived from a dihydroxy-substituted aromatichydrocarbon and x has a value of about 10 to about 100. In someparticular embodiments x may have a value in a range of between about 30and about 100 and in other particular embodiments x may have a value ina range of between about 30 and about 60.

In particular embodiments Ar comprises m-phenylene, p-phenylene,4,4′-biphenylene, 4,4′-bi(3,5-dimethyl)-phenylene,2,2-bis(4-phenylene)propane,6,6′-(3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indan]) and similar radicalssuch as those derived from the dihydroxy-substituted aromatichydrocarbons disclosed by name or formula (generic or specific) in U.S.Pat. No. 4,217,438. In other particular embodiments thedihydroxy-substituted aromatic hydrocarbon from which Ar is derivedincludes, but is not limited to4,4′-(3,3,5-trimethylcyclohexylidene)diphenol;4,4′-bis(3,5-dimethyl)diphenol,1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane;4,4-bis(4-hydroxyphenyl)heptane; 2,4′-dihydroxydiphenylmethane;bis(2-hydroxyphenyl)methane; bis(4-hydroxyphenyl)methane;bis(4-hydroxy-5-nitrophenyl)methane;bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane;1,1-bis(4-hydroxyphenyl)ethane; 1,2-bis(4-hydroxyphenyl)ethane;1,1-bis(4-hydroxy-2-chlorophenyl)ethane;2,2-bis(4-hydroxyphenyl)propane;2,2-bis(3-phenyl-4-hydroxyphenyl)propane;2,2-bis(4-hydroxy-3-methylphenyl)propane;2,2-bis(4-hydroxy-3-ethylphenyl)propane;2,2-bis(4-hydroxy-3-isopropylphenyl)propane;2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane;3,5,3′,5′-tetrachloro-4,4′-dihydroxyphenyl)propane;bis(4-hydroxyphenyl)cyclohexylmethane;2,2-bis(4-hydroxyphenyl)-1-phenylpropane; 2,4′-dihydroxyphenyl sulfone;dihydroxy naphthalene, 2,6-dihydroxy naphthalene; hydroquinone;resorcinol; C₁₋₃ alkyl-substituted resorcinols;2,2-bis-(4-hydroxyphenyl)butane;2,2-bis-(4-hydroxyphenyl)-2-methylbutane;1,1-bis-(4-hydroxyphenyl)cyclohexane; bis-(4-hydroxyphenyl);bis-(4-hydroxyphenyl)sulphide;2-(3-methyl-4-hydroxyphenyl-2-(4-hydroxyphenyl)propane;2-(3,5-dimethyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane;2-(3-methyl-4-hydroxyphenyl)-2-(3,5-dimethyl-4-hydroxyphenyl)propane;bis-(3,5-dimethylphenyl-4-hydroxyphenyl)methane;1,1-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)ethane;2,2-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)propane;2,4-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)-2-methylbutane;3,3-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)pentane;1,1-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)cyclopentane;1,1-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)cyclohexane;bis-(3,5-dimethylphenyl-4-hydroxyphenyl)sulphide,3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol,1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol,2,2,2′,2′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]-6,6′-diol,and mixtures thereof. In a particular embodiment thedihydroxy-substituted aromatic hydrocarbon from which Ar is derived isbisphenol A. As the siloxane oligomers shown in Formulas XII and XVI arealso hydroxy terminated, they may also be substituted for a portion ofthe resorcinol to be introduced into the chain by reaction with thedicarboxylic acid dichloride.

In an embodiment, the soft block moiety is introduced into the polymerduring synthesis of the organic carbonate group. Preferably, thesoft-block moiety comprises a bisphenol functionalized with an aliphaticester. More preferably, the bisphenol functionalized with an aliphaticester has the structure as shown in Formula XIII,

where R¹⁶ comprises a C₄₋₂₀ aliphatic radical. In an embodiment, thealiphatic ester comprises at least eight carbons. Preferably, thesoft-block moiety comprises n-octadecyl-4,4-bis(4-hydroxyphenyl)valerate(C18-BPA-PC), 2-ethylhexyl-4,4-bis(4-hydroxyphenyl)valerate,n-hexadecyl-4,4-bis(4-hydroxyphenyl)valerate,dodecyl-4,4,-bis(4-hydroxyphenyl)valerate, and the like.

In yet another embodiment, the soft-block moiety comprises an aliphaticmoiety introduced into the polymer using a chainstopper comprising analiphatic tail as shown in Formula XIV,

where R₁₇ is a C₆–C₂₀ alkyl and X is O or CH₂, such as p-nonylphenol orp-dodecylphenol.

In another aspect, the present invention comprises a resorcinol esterpolycarbonate polymer comprising at least one soft-block moietyincorporated into a resorcinol phthalate-co-bisphenol A-polycarbonatecopolymer substantially free of anhydride linkages, wherein theresorcinol phthalate-co-bisphenol A-polycarbonate copolymer comprisesthe structural unit of Formula IV, as defined herein, and the soft-blockcomprises Formula XI, as defined herein. In an embodiment, R^(x) ofFormula IV comprises a divalent organic radical derived from a bisphenolof Formula VIII as described herein. In one embodiment, the soft-blockcomprises an aliphatic polyester or a polycarbonate oligomer. In anotherembodiment, the soft-block comprises a polyethylene oligomer. In yetanother embodiment, the soft-block comprises poly(tetrahydrofuran)diol.The soft-block may also comprise an o,p-mixture of citronellylcitronellate diphenol (CCDP).

In another aspect, the present invention comprises a resorcinol esterpolycarbonate polymer comprising at least one soft-block moietyincorporated into a resorcinol phthalate-co-bisphenol A-polycarbonatecopolymer substantially free of anhydride linkages, wherein theresorcinol phthalate-co-bisphenol A-polycarbonate copolymer comprisesthe structural unit of Formula IV, as defined herein, and the soft-blockcomprises Formula X, as defined herein. In an embodiment, R^(x) ofFormula IV comprises a divalent organic radical derived from a bisphenolof Formula VIII as described herein. In an embodiment, the soft-blockcomprises an aliphatic ester. Preferably, the ester comprises at leastsix, and more preferably at least eight, and even more preferably, atleast ten carbon atoms.

In another aspect, the present invention comprises a resorcinol esterpolycarbonate polymer comprising at least one soft-block moietyincorporated into a resorcinol phthalate-co-bisphenol A-polycarbonatecopolymer substantially free of anhydride linkages, wherein theresorcinol phthalate-co-bisphenol A-polycarbonate copolymer comprisesthe structural unit of Formula IV as defined herein, and the soft-blockcomprises either a siloxane oligomer derived from the dihydroxy compoundas shown in Formula XII, where q is in one embodiment 1–99, in anotherembodiment 30–70, in yet another embodiment, 1–20, and in anotherparticular embodiment, 10–20,

or a siloxane oligomer derived from the dihydroxy compound as shown inFormula XVI, wherein the moiety Ar is derived from adihydroxy-substituted aromatic hydrocarbon and x has a value of about 10to about 100:

In another aspect, the present invention comprises a resorcinol esterpolycarbonate polymer comprising at least one soft-block moietyincorporated into a resorcinol phthalate-co-bisphenol A-polycarbonatecopolymer substantially free of anhydride linkages, wherein theresorcinol phthalate-co-bisphenol A-polycarbonate copolymer comprisesthe structural unit of Formula IV, as defined herein, and the soft-blockcomprises a bisphenol functionalized with an aliphatic ester as shown inFormula XIII,

where R¹⁶ comprises a C₄₋₂₀ aliphatic radical. In an embodiment, R^(x)of Formula IV comprises a divalent organic radical derived from abisphenol of Formula VIII as described herein.

In another aspect, the present invention comprises a resorcinol esterpolycarbonate polymer comprising at least one soft-block moietyincorporated into a resorcinol phthalate-co-bisphenol A-polycarbonatecopolymer substantially free of anhydride linkages, wherein theresorcinol phthalate-co-bisphenol A-polycarbonate copolymer comprisesthe structural unit of Formula IV, and the soft-block comprises analiphatic moiety introduced into the polymer using a chainstoppercomprising an aliphatic tail as shown in Formula XIV,

wherein R¹⁷ comprises a C₆–C₂₀ alkyl and X is —O— or —CH₂—. For example,in an embodiment, the soft-block moiety comprises p-nonylphenol orp-dodecylphenol. In an embodiment, R^(x) of Formula IV comprises adivalent organic radical derived from a bisphenol of Formula VIII asdescribed herein.

The polymer may comprise varying levels of the soft-block moietydepending upon the characteristics that are required. Preferably, thesoft-block moiety comprises 0.1–25% by weight of the polymer. Morepreferably, the soft-block moiety comprises 1–20% by weight of thepolymer. Even more preferably, the soft-block moiety comprises 2–10% byweight of the polymer.

One of the advantages of incorporating soft-block moieties is theresultant decrease in melt viscosity that occurs upon incorporation ofthe soft-block. In an embodiment, the reduction in melt viscosity uponaddition of the soft-block moiety comprises greater than 5% at 250° C.,more preferably, greater that 10% at 250° C., and more preferably,greater than 20% at 250° C.

Preferably, the reduction in melt viscosity is associated with minimalreduction in glass transition temperature. Thus, the polymers of thepresent invention preferably comprise a glass transition temperature(Tg) greater than about 120° C., and more preferably, greater than 125°C., and even more preferably, greater than 130° C.

Thus, in one embodiment, the present invention comprises a thermostable,weatherable, resorcinol ester polycarbonate polymer having good flowcharacteristics wherein said polymer comprises: (a) a resorcinol arylatepolyester chain substantially free of anhydride linkages; (b) at leastone organic carbonate group; and (c) at least one soft-block chemicalmoiety. For example, copolyesters comprising resorcinol iso- andterephthalate polyester chain members in combination with diacid or diolalkylene chain members (so-called “soft-block” chain members) aredisclosed in commonly owned U.S. Pat. No. 5,916,997. These copolymershave excellent weatherability and flexibility. Copolyestercarbonatescomprising resorcinol iso- and terephthalate polyester chain members incombination with carbonate chain members are disclosed in commonlyowned, co-pending application Ser. No. 09/416,529, filed Oct. 12, 1999.These copolymers also have excellent weatherability and are compatiblewith polycarbonates in blends. Poly(resorcinol isophthalate) containinga soft-block comprised of sebacic acid functionalities have also beendisclosed in U.S. Pat. No. 6,143,839. Still, there has not been aprevious description of poly(resorcinol phthalate-co-polycarbonate)(“poly(RP-co-PC)”) materials containing soft-block moieties.

In an embodiment, the polymers of the invention have good thermalstability. Thermal stability within the context of the present inventionrefers to resistance of a polymer to molecular weight degradation underthermal conditions. Thus, a polymer with poor thermal stability showssignificant molecular weight degradation under thermal conditions, suchas during extrusion, molding, thermoforming, hot-pressing, and likeconditions. Molecular weight degradation may also be manifest throughcolor formation and/or in the degradation of other properties such asweatherability, gloss, mechanical properties, and/or thermal properties.Molecular weight degradation can also cause significant variation inprocessing conditions as the melt viscosity changes.

In one of its aspects, the method of the present invention providesthermally stable polymers comprising arylate polyester chain members.These chain members comprise at least one diphenol residue incombination with at least one aromatic dicarboxylic acid residue. In oneembodiment, the diphenol residue of the arylate polyester chain memberis derived from a 1,3-dihydroxybenzene moiety, as illustrated in FormulaI,

commonly referred to throughout this specification as resorcinol orresorcinol moiety. Resorcinol or resorcinol moiety as used within thecontext of the present invention should be understood to include bothunsubstituted 1,3-dihydroxybenzene and substituted 1,3-dihydroxybenzenesunless explicitly stated otherwise.

In Formula I, R^(y) is at least one of C₁₋₁₂ alkyl or halogen, and n is0–3. Alkyl groups, if present, are typically straight-chain, branched,or cyclic alkyl groups, and are most often located in the ortho positionto both oxygen atoms although other ring locations are contemplated.Suitable C₁₋₁₂ alkyl groups include, but are not limited to, methyl,ethyl, n-propyl, isopropyl, butyl, iso-butyl, t-butyl, hexyl,cyclohexyl, nonyl, decyl, and aryl-substituted alkyl, including benzyl.In a particular embodiment, an alkyl group is methyl. Suitable halogengroups are bromo, chloro, and fluoro. The value for n in variousembodiments may be 0–3, in some embodiments 0–2, and in still otherembodiments 0–1. In one embodiment, a resorcinol moiety is2-methylresorcinol. In another embodiment the resorcinol moiety is anunsubstituted resorcinol moiety in which n is zero.

Suitable dicarboxylic acid residues include aromatic dicarboxylic acidresidues derived from monocyclic moieties. In various embodimentssuitable dicarboxylic acid residues include those derived fromisophthalic acid, terephthalic acid, or mixtures of isophthalic andterephthalic acids. Suitable dicarboxylic acid residues also includethose derived from polycyclic moieties, illustrative examples of whichinclude diphenyl dicarboxylic acid, diphenylether dicarboxylic acid, andnaphthalenedicarboxylic acid, especially naphthalene-2,6-dicarboxylicacid. In some embodiments, the aromatic dicarboxylic acid residues arederived from mixtures of isophthalic and/or terephthalic acids astypically illustrated in Formula II:

Therefore, in one embodiment, the present invention provides thermallystable polymers comprising resorcinol arylate polyester chain members astypically illustrated in Formula III,

wherein R^(y) and n are as previously defined.

The copolyester polycarbonates of the present invention include thosecomprising arylate and organic carbonate blocks as illustrated inFormula IV,

where as above, R^(y) is at least one of C₁₋₁₂ alkyl or halogen, n is0–3, m is at least about 8, p is at least about 10, and R^(x) is atleast one divalent organic radical, wherein the organic radicalcomprises an aromatic, aliphatic or a cycloaliphatic radical.

The arylate blocks have a degree of polymerization (DP), represented bym, in one embodiment of at least about 4, in another embodiment of atleast about 10, in another embodiment of at least about 20 and in stillanother embodiment of about 30–150. The DP of the organic carbonateblocks, represented by p, is in one embodiment generally at least about10, in another embodiment at least about 20 and in still anotherembodiment about 50–200. The distribution of the blocks may be such asto provide a copolymer having any desired weight proportion of arylateblocks in relation to carbonate blocks. In general, the content ofarylate blocks is in one embodiment about 10–95% by weight and inanother embodiment about 50–95% by weight.

In the organic carbonate blocks, each R^(x) is independently a divalentorganic radical. In various embodiments said radical comprises at leastone dihydroxy-substituted aromatic hydrocarbon, and at least about 60mole percent of the total number of R^(x) groups in the polymer arearomatic organic radicals and the balance thereof are aliphatic,alicyclic, or aromatic radicals. In some embodiments suitable R^(x)radicals comprise those described hereinabove for Ar groups of FormulaXVI and include, but are not limited to, m-phenylene, p-phenylene,4,4′-biphenylene, 4,4′-bi(3,5-dimethyl)-phenylene,2,2-bis(4-phenylene)propane,6,6′-(3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indan]) and similar radicalssuch as those which correspond to the dihydroxy-substituted aromatichydrocarbons disclosed by name or formula (generic or specific) in U.S.Pat. No. 4,217,438.

In some embodiments each R^(x) is an aromatic organic radical and inother embodiments a radical of Formula V:-A¹-Y-A²-   (Formula V)wherein each A¹ and A² is a monocyclic divalent aryl radical and Y is abridging radical in which one or two carbon atoms separate A¹ and A².The free valence bonds in Formula V are usually in the meta or parapositions of A¹ and A² in relation to Y. Compounds in which R^(x) hasFormula V are bisphenols, and for the sake of brevity the term“bisphenol” is sometimes used herein to designate thedihydroxy-substituted aromatic hydrocarbons. It should be understood,however, that non-bisphenol compounds of this type may also be employedas appropriate.

In Formula V, A¹ and A² typically represent unsubstituted phenylene orsubstituted derivatives thereof, illustrative substituents (one or more)being alkyl, alkenyl, and halogen (particularly bromine). In oneembodiment, unsubstituted phenylene radicals are preferred. Both A¹ andA² are often p-phenylene, although both may be o- or m-phenylene or oneo- or m-phenylene and the other p-phenylene.

The bridging radical, Y, is one in which one or two atoms separate A¹from A². In a particular embodiment, one atom separates A¹ from A².Illustrative radicals of this type are —O—, —S—, —SO— or —SO₂—,methylene, cyclohexyl methylene, 2-[2.2.1]-bicycloheptyl methylene,ethylene, isopropylidene, neopentylidene, cyclohexylidene,cyclopentadecylidene, cyclododecylidene, adamantylidene, and likeradicals.

In some embodiments, gem-alkylene (commonly known as “alkylidene”)radicals are preferred. Also included, however, are unsaturatedradicals. In some embodiments, the preferred bisphenol is2,2-bis(4-hydroxyphenyl)propane (bisphenol-A or BPA), in which Y isisopropylidene and A¹ and A² are each p-phenylene. Depending upon themolar excess of resorcinol moiety present in the reaction mixture, R^(x)in the carbonate blocks may at least partially comprise resorcinolmoiety. In other words, in some embodiments of the invention, carbonateblocks of Formula IV may comprise a resorcinol moiety in combinationwith at least one other dihydroxy-substituted aromatic hydrocarbon.

Diblock, triblock, and multiblock copolyestercarbonates are encompassedin the present invention. The chemical linkages between blockscomprising resorcinol arylate chain members and blocks comprisingorganic carbonate chain members may comprise at least one of:

-   -   (a) an ester linkage between a suitable dicarboxylic acid        residue of an arylate moiety and an —O—R^(x)—O— moiety of an        organic carbonate moiety, for example as typically illustrated        in Formula VI, wherein R^(x) is as previously defined:

-   -   and (b) a carbonate linkage between a diphenol residue of a        resorcinol arylate moiety and a —(C═O)—O— moiety of an organic        carbonate moiety as shown in Formula VII,

wherein R^(y) and n are as previously defined.

In a preferred embodiment, bisphenol is used to generate thepolycarbonate wherein the bisphenol group bisphenols have Formula VIII

wherein R³–R¹⁰ are independently a hydrogen atom, halogen atom, nitrogroup, cyano group, C₁–C₃₀ alkyl group, C₄–C₃₀ cycloalkyl group, orC₆–C₃₀ aryl group, a C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy or C₆–C₃₀aryloxy; W is a direct bond, or an oxygen atom, sulfur atom, C═O group,SO₂ group, C₁–C₂₀ aliphatic radical, C₆–C₂₀ aromatic radical, C₆–C₂₀cycloaliphatic radical, or the group,

wherein R¹¹ and R¹² are independently a hydrogen atom, C₁–C₂₀ alkylgroup, C₄–C₂₀ cycloalkyl group, or C₄–C₂₀ aryl group; or R¹¹ and R¹²together form a C₄–C₂₀ cycloaliphatic ring which is optionallysubstituted by one or more C₁–C₂₀ alkyl, C₆–C₂₀ aryl, C₅–C₂₁ arylalkyl,C₅–C₂₀ cycloalkyl groups or a combination thereof.

As described herein, in a preferred embodiment, the carbonate blockscomprise a bisphenol. Suitable bisphenols VIII are illustrated by2,2-bis(4-hydroxyphenyl)propane (bisphenol A);2,2-bis(3-chloro-4-hydroxyphenyl)propane;2,2-bis(3-bromo-4-hydroxyphenyl)propane;2,2-bis(4-hydroxy-3-methylphenyl)propane;2,2-bis(4-hydroxy-3-isopropylphenyl)propane;2,2-bis(3-t-butyl-4-hydroxyphenyl)propane;2,2-bis(3-phenyl-4-hydroxyphenyl)propane;2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane;2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane;2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane;2,2-bis(3-chloro-4-hydroxy-5-methylphenyl)propane;2,2-bis(3-bromo-4-hydroxy-5-methylphenyl)propane;2,2-bis(3-chloro-4-hydroxy-5-isopropylphenyl)propane;2,2-bis(3-bromo-4-hydroxy-5-isopropylphenyl)propane;2,2-bis(3-t-butyl-5-chloro-4-hydroxyphenyl)propane;2,2-bis(3-bromo-5-t-butyl-4-hydroxyphenyl)propane;2,2-bis(3-chloro-5-phenyl-4-hydroxyphenyl)propane;2,2-bis(3-bromo-5-phenyl-4-hydroxyphenyl)propane;2,2-bis(3,5-diisopropyl-4-hydroxyphenyl)propane;2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane;2,2-bis(3,5-diphenyl-4-hydroxyphenyl)propane;2,2-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)propane;2,2-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)propane;2,2-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)propane;2,2-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)propane;2,2-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)propane;1,1-bis(4-hydroxyphenyl)cyclohexane;1,1-bis(3-chloro-4-hydroxyphenyl)cyclohexane;1,1-bis(3-bromo-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxy-3trimethylcyclohexane;1,1-bis(3-bromo-5-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(3,5-diisopropyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(3,5-di-t-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)-3,3,5-trimethylcyclohexane;1,1-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)-3,3,5-trimethylcyclohexane;1,1-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;4,4′-dihydroxy-1,1-biphenyl; 4,4′-dihydroxy-3,3′-dimethyl-1,1-biphenyl;4,4′-dihydroxy-3,3′-dioctyl-1,1-biphenyl; 4,4′-dihydroxydiphenylether;4,4′-trimethylcyclohexane;1,1-bis(3-bromo-5-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(3,5-diisopropyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(3,5-di-t-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)-3,3,5-trimethylcyclohexane;1,1-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)-3,3,5-trimethylcyclohexane;1,1-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;1,1-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;4,4′-dihydroxy-1,1-biphenyl; 4,4′-dihydroxy-3,3′-dimethyl-1,1-biphenyl;4,4′-dihydroxy-3,3′-dioctyl-1,1-biphenyl; 4,4′-dihydroxydiphenylether;4,4′-dihydroxydiphenylthioether;1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene;1,3-bis(2-(4-hydroxy-3-methylphenyl)-2-propyl)benzene;1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene and1,4-bis(2-(4-hydroxy-3-methylphenyl)-2-propyl)benzene. Bisphenol A ispreferred.

Poly(resorcinol arylate-polycarbonate) copolymers possess many desirableproperties such as, but not limited to, weatherability, flexibility,thermostability, and resistance to physical and chemical degradation.The present invention relies on the use of soft-block functionalities toprovide reduced melt viscosity and improved flow characteristics topoly(resorcinol arylate-polycarbonate) polymers. Thus, the presentinvention teaches the incorporation of melt block functionalities intopoly(resorcinol arylate-polycarbonate polymers.

The term soft-block as used herein, indicates that some segments of thepolymers are made from non-aromatic monomer units. Such non-aromaticmonomer units are generally aliphatic and are known to impartflexibility to the soft-block-containing polymers. The copolymersinclude those comprising structural units as described by Formulas IX,X, XI, XII, XIII, XIV, and XVI. It is contemplated, however, that othersimilar or equivalent structures may be included in the polymer chain toincrease the aliphatic nature (and flexibility) of the final product.For example, oligomers comprising functional groups other than oxygenand siloxane may be employed. Also, the present invention contemplatesthat more that one type of soft-block polymer may be used. For example,it is contemplated that poly(resorcinol arylate-polycarbonate) polymersmay be made using at least a portion of the chain stoppers comprising analiphatic tail along with at least a portion of bisphenol substitutedwith an aliphatic ester and/or an aliphatic ester substituted for aportion of the dicarboxylic acid dichloride used to produce the chain.

In another aspect, the present invention comprises a method of making aresorcinol ester polycarbonate polymer having good flow characteristicscomprising: (a) generating a resorcinol arylate polyester; (b)conducting an interfacial polymerization in the presence of at least onedivalent organic radical to generate a poly(resorcinolarylate-co-polycarbonate) comprising an organic carbonate group; and (c)incorporating at least one soft-block chemical moiety into the polymerduring step (a) or step (b) or both.

In an embodiment, the resorcinol arylate polyester chain comprises thecondensation of at least one resorcinol moiety with at least onedicarboxylic acid dichloride, wherein the dicarboxylic acid residuescomprise monocyclic moieties or polycyclic aromatic moieties.

Preferably, the resorcinol arylate polyester chain is substantially freeof anhydride linkages. More preferably, and to generate an arylatepolyester chain is substantially free of anhydride linkages, theresorcinol arylate polyester chain comprises the interfacialcondensation of at least one resorcinol moiety with at least onedicarboxylic acid dichloride while maintaining the pH between 3 and 8.5through the presence of an acid acceptor, wherein the total molar amountof acid chloride groups is stoichiometrically deficient relative to thetotal molar amount of phenolic groups. Even more preferably, thestoichiometric ratio of total phenolic groups to total acid chloridegroups for generation of the resorcinol arylate polyester chain is1.5–1.01:1.

In an embodiment, the resorcinol moiety used to generate the resorcinolarylate polyester chain comprises compounds of Formula I:

wherein R^(y) is at least one of C₁₋₁₂ alkyl or halogen, and n is 0–3.Preferably, the resorcinol moiety used to generate the resorcinolarylate polyester chain comprises unsubstituted resorcinol, 2-methylresorcinol, and mixtures thereof.

In an embodiment, the dicarboxylic acid residues comprise monocyclic orpolycyclic aromatic groups. Preferably, the dicarboxylic acid dichloridecomprises isophthaloyl dichloride, terephthaloyl dichloride,naphthalene-2,6-dicarboxylic acid dichloride and mixtures thereof.

In an embodiment, the resorcinol ester polycarbonate polymer comprisesstructure as illustrated in Formula IV:

where R^(y) is at least one of C₁₋₁₂ alkyl or halogen, n is 0–3, m is atleast about 8, p is at least about 10, and R^(x) is at least onedivalent organic radical, wherein the organic radical comprises anaromatic, aliphatic or cycloaliphatic radical.

Preferably, R^(x) comprises a divalent organic radical derived from abisphenol of Formula VIII:

wherein R³–R¹⁰ are independently a hydrogen atom, halogen atom, nitrogroup, cyano group, C₁–C₃₀ alkyl group, C₄–C₃₀ cycloalkyl group, orC₆–C₃₀ aryl group, a C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy or C₆–C₃₀aryloxy; W is a direct bond, or an oxygen atom, sulfur atom, C═O group,SO₂ group, C₁–C₂₀ aliphatic radical, C₆–C₂₀ aromatic radical, C₆–C₂₀cycloaliphatic radical, or the group,

wherein R¹¹ and R¹² are independently a hydrogen atom, C₁–C₂₀ alkylgroup, C₄–C₂₀ cycloalkyl group, or C₄–C₂₀ aryl group; or R¹¹ and R¹²together form a C₄–C₂₀ cycloaliphatic ring which is optionallysubstituted by one or more C₁–C₂₀ alkyl, C₆–C₂₀ aryl, C₅–C₂₁ aralkyl,C₅–C₂₀ cycloalkyl groups, or a combination thereof.

In an embodiment, the soft-block moiety comprises structural units ofFormulas IX, X or XI:

wherein R^(y) is at least one of C₁₋₁₂ alkyl or halogen, and n is 0–3; Zis a divalent aliphatic radical, or a C₃₋₂₀ straight chain alkylene suchas —(CH₂)₂₀—; and s is 0–10, R¹³ is a C₃₋₂₀ straight chain alkylene, aC₃₋₁₀ branched alkylene, a C₄₋₁₀ cyclo- or bicycloalkylene group,—CH₂(CH₂OCH₂)_(r)CH₂—, where r is 1–20, or a polyester comprising theformula —CH₂([CH₂]_(b)O[CH₂]_(b))_(c)CH₂— where b is 1–3 and c is 1–10;and R¹⁴ and R¹⁵ each independently represent:

In Formulas IX, X and XI, as elsewhere herein, wavy lines representpolymer chain structure.

In an embodiment, the soft-block moiety comprises an aliphatic ester. Inan embodiment, the aliphatic ester comprises at least six carbons. Morepreferably, the aliphatic ester comprises at least eight carbons, andeven more preferably, the aliphatic ester comprises at least tencarbons. Preferably, the aliphatic ester is introduced into the polymerby co-reaction of an aliphatic diacid or diacid chloride with anisophthaloyl or terephthaloyl chloride for polymerization with theresorcinol monomer units. More preferably, the soft-block moietycomprises carboxy-terminated polybutadiene, carboxy-terminatedbutadiene-acrylonitrile copolymer, adipoyl chloride, sebacoyl chloride,or dodecanoyl chloride.

In an embodiment, the soft-block moiety comprises at least one hydroxyend-group. Preferably, the hydroxy terminated soft-block moiety issubstituted for a portion of the resorcinol moiety used to produce theresorcinol arylate chain.

In an embodiment, the soft-block moiety comprises oligomers ofdiethylene glycol, tetraethylene glycol, or low molecular weightpolyethylene glycol substituted for a portion of the resorcinol used togenerate the chain to react with the dicarboxylic acid dichloride duringsynthesis of the polymer. Preferably, the molecular weight of thepolyethylene glycol is less than 600 Mw.

In another embodiment, the soft-block moiety comprises ahydroxy-terminated aliphatic polyester or polycarbonate oligomer,wherein the hydroxy-terminated aliphatic polyester or polycarbonateoligomer is substituted for a portion of the resorcinol used to generatethe chain to react with the dicarboxylic acid dichloride duringsynthesis of the polymer.

In yet another embodiment, the soft-block moiety comprisespoly(tetrahydrofuran) diol or alternatively, an o,p-mixture ofcitronellyl citronellate diphenol (CCDP). Preferably, thepoly(tetrahydrofuran) diol or CCDP also reacts with the dicarboxylicacid dichloride for incorporation into the polymer.

The present invention also provides for various heterofunctionalsoft-block moieties. Thus, in another embodiment, the soft-block moietycomprises the reaction residue of a siloxane oligomer as shown inFormula XII,

where q is in one embodiment 1–99, and in another embodiment 30–70,specifically 20–60. In one particular embodiment q has a value of 1–20.In another particular embodiment q has a value of 10–20.

In an embodiment, the siloxane oligomer may range from one to at leasttwenty siloxane units. Thus, the siloxane oligomer may compriseα,ω(3-(4-hydroxy-3-methoxy)-propyl)-deca(dimethylsiloxane) (ED10E),1,3(bis-3-(4-hydroxy-3-methoxy)-propyl)-1,1,3,3,-tetramethyl disiloxane(EMME), or oligomers of similar structure.

In still another embodiment the soft-block moiety comprises a siloxaneoligomer derived from a residue of a dihydroxy compound as shown inFormula XVI, wherein the moiety Ar is derived from adihydroxy-substituted aromatic hydrocarbon and x has a value of about 10to about 100:

As the siloxane oligomers shown in Formulas XII and XVI are also hydroxyterminated, they may also be substituted for a portion of the resorcinolto be introduced into the chain by reaction with the dicarboxylic aciddichloride.

In an embodiment, the soft block moiety is introduced into the polymerduring syntheses of the organic carbonate group. Preferably, thesoft-block moiety comprises a bisphenol functionalized with an aliphaticester. More preferably, the bisphenol functionalized with an aliphaticester has the structure as shown in Formula XIII,

where R¹⁶ comprises an C₄₋₂₀ aliphatic radical. In an embodiment, thealiphatic ester comprises at least eight carbons. Preferably, thesoft-block moiety comprises n-octadecyl-4,4-bis(4-hydroxyphenyl)valerate(C18-BPA-PC), 2-ethylhexyl-4,4-bis(4-hydroxyphenyl)valerate,n-hexadecyl-4,4-bis(4-hydroxyphenyl)valerate,dodecyl-4,4,-bis(4-hydroxyphenyl)valerate, and the like.

In yet another embodiment, the soft-block moiety comprises an aliphaticmoiety introduced into the polymer using a chainstopper comprising analiphatic tail as shown in Formula XIV,

where R₁₇ is a C₆–C₂₀ alkyl and X is —O— or —CH₂—, such as p-nonylphenolor p-dodecylphenol.

The polymer may comprise varying levels of the soft-block moietydepending upon the characteristics that are required. Preferably, thesoft-block moiety comprises 0.1–25% of the polymer. More preferably, thesoft-block moiety comprises 1–20% of the polymer. Even more preferably,the soft-block moiety comprises 2–10% of the polymer.

One of the advantages of incorporating soft-block moieties is theresultant decrease in melt viscosity that occurs upon incorporation ofthe soft-block. In an embodiment, the reduction in melt viscosity uponaddition of the soft-block moiety comprises greater than 5% at 250° C.,more preferably, greater that 10% at 250° C., and more preferably,greater than 20% at 250° C.

Preferably, the reduction in melt viscosity is preferably associatedwith minimal reduction in glass transition temperature. Preferably, thepolymers of the present invention comprise a glass transitiontemperature (Tg) greater than about 120° C., and more preferably,greater than 125° C., and even more preferably, greater than 130° C.

Thus, the present invention provides methods of making a resorcinolester polycarbonate polymers that incorporate soft-block moieties andthus have good flow characteristics.

For example, in an embodiment, resorcinol phthalate-co-polycarbonate(RP-co-PC) copolymers are made via a two-step, one-pot process (e.g.Equation (1)). In the first step, resorcinol and chainstopper arereacted with a mixture of dicarboxylic dichlorides in CH₂Cl₂ using Et₃Nas a catalyst with NaOH to control the pH, forming a low-molecularweight resorcinol phthalate polymer to give a compound of Formula III:

A dihydroxy compound, for example a bisphenol, is then added to theresorcinol arylate polyester, and the mixture subjected to phosgenationunder typical polycarbonate conditions, to form a RP-co-PC copolymercompound. The soft-block moiety can be included in the polymer (duringsteps (a) or (b) or both, using various strategies as described herein.

Thus, in one aspect, the present invention describes a method to makepoly(resorcinol arylate polycarbonate) copolymers comprising soft-blockmoieties. In another embodiment, the method may comprise a two step, twopot process, wherein the products of each of steps a and b are isolated.

Preferably, the arylate polyester chain polymer members comprise atleast one diphenol residue in combination with at least one aromaticdicarboxylic acid residue. The diphenol residue may be derived from a1,3-dihydroxybenzene moiety, as illustrated in Formula I:

wherein R^(y) is at least one of C₁₋₁₂ alkyl or halogen, and n is 0–3.Alkyl groups, if present, are typically straight-chain, branched, orcyclic alkyl groups, and are most often located in the ortho position toboth oxygen atoms although other ring locations are contemplated.Suitable C₁₋₁₂ alkyl groups include, but are not limited to, methyl,ethyl, n-propyl, isopropyl, butyl, iso-butyl, t-butyl, hexyl,cyclohexyl, nonyl, decyl, and aryl-substituted alkyl, including benzyl.In a particular embodiment, an alkyl group is methyl. Suitable halogengroups are bromo, chloro, and fluoro. The value for n in variousembodiments may be 0–3, in some embodiments 0–2, and in still otherembodiments 0–1. In one embodiment a resorcinol moiety is2-methylresorcinol. In another embodiment the resorcinol moiety is anunsubstituted resorcinol moiety in which n is zero.

Suitable dicarboxylic acid dichlorides may comprise aromaticdicarboxylic acid dichlorides derived from monocyclic moieties,illustrative examples of which include isophthaloyl dichloride,terephthaloyl dichloride, or mixtures of isophthaloyl and terephthaloyldichlorides. Suitable dicarboxylic acid dichlorides may also comprisearomatic dicarboxylic acid dichlorides derived from polycyclic moieties,illustrative examples of which include diphenyl dicarboxylic aciddichloride, diphenylether dicarboxylic acid dichloride, andnaphthalenedicarboxylic acid dichloride, especiallynaphthalene-2,6-dicarboxylic acid dichloride, or from mixtures ofmonocyclic and polycyclic aromatic dicarboxylic acid dichlorides. In oneembodiment the dicarboxylic acid dichloride comprises mixtures ofisophthaloyl and/or terephthaloyl dichlorides as typically illustratedin Formula XV:

Either or both of isophthaloyl and terephthaloyl dichlorides may bepresent. In some embodiments the dicarboxylic acid dichlorides comprisemixtures of isophthaloyl and terephthaloyl dichloride in a molar ratioof isophthaloyl to terephthaloyl of about 0.25–4.0:1; in otherembodiments the molar ratio is about 0.4–2.5:1; and in still otherembodiments the molar ratio is about 0.67–1.5:1.

The resorcinol phthalate-co-polycarbonate copolymers of the presentinvention are illustrated in Formula IV,

where as above, R^(y) is at least one of C₁₋₁₂ alkyl or halogen, n is0–3, m is at least about 8, p is at least 10, and R^(x) is at least onedivalent organic radical as described above. In an embodiment, m is 4.

The present invention relies on the use of soft-block functionalities toprovide reduced melt viscosity and improved flow characteristics toRP-co-PC polymers. Thus, the present invention teaches the incorporationof melt block functionalities into RP-co-PC polymers. The melt blockfunctionalities include those comprising structural units as describedby Formulas IX, X, XI, XII, XIII, XIV and XVI. However, other similar orequivalent structures may be included in the polymer chain to increasethe aliphatic nature (and flexibility) of the final product. Forexample, oligomers comprising heteroatoms other than oxygen and/orsiloxane may be employed. Also, the present invention contemplates thatmore than one type of soft-block polymer may be used. For example, it iscontemplated that polymers may incorporate chain stoppers having analiphatic tail along with at least a portion of the bisphenol modifiedwith an aliphatic ester group. Alternatively, or additionally,polyethylene glycol may be substituted for a portion of the resorcinoland an aliphatic ester substituted for a portion of the dicarboxylicacid dichloride used for the polymerization using the methods describedbelow.

The present invention comprises various methods by which the soft-blockmoiety may be incorporated into a resorcinol phthalate-co-polycarbonate(RP-coPC) polymer. In an embodiment, the method uses a chainstopper witha lengthy aliphatic tail. This technique is both simple to implement andeffective. For example, p-nonylphenol or p-dodecylphenol may substitutedfor a normal chainstopper such as phenol in a normal RP-co-PCpolymerization reaction (Equation 1). In an embodiment, incorporation ofthe soft-block moiety results in a large decrease in melt viscosity andflow energy with only a modest reduction in glass transition temperature(Tg).

In another embodiment, diols such as polyethylene glycol oligomers maybe used as soft-block moieties. In an embodiment, a hydroxy-terminatedoligomer is pre-reacted with the iso/terephthaloyl chloride in CH₂Cl₂using stoichiometric triethylamine, forming a polyethylene glycololigomer terminated with an iso/terephthaloyl chloride end group asshown in Equation 2, below. In an embodiment, the number of ethyleneglycol units (r) ranges from 2–10. Resorcinol is then be added, and theremainder of the RP-co-PC polymerization carried out under usualinterfacial polymerization conditions. In an embodiment, the moldedpolymers are clear and nearly colorless. Lower molecular weight (Mw)oligomers are very effective at reducing melt viscosity, flow energy,and Tg. Lower molecular weight polyethylene glycols such as diethyleneglycol (DEG), tetraethylene glycol (TEG), and PEG 300, may be preferablesince the higher molecular weight polyethylene glycols can result in theformation of very high molecular weight species.

Other diols may be used. In an embodiment, the diol used as a soft-blockmoiety is an o,p mixture of citronellyl citronellate diphenol.

In yet another embodiment, poly(tetrahydrofuran)-diol) (polyTHF-diol)reduces viscosity as well as Tg, even at a level of only 2% by weight.

The present invention also provides for heterofunctional soft-blockmoieties. Thus, in another embodiment, the soft-block moiety comprises asiloxane oligomer. The siloxane oligomer may range from one to at leastten siloxane units. Thus, the siloxane oligomer may compriseα,ω(3-(4-hydroxy-3-methoxy)-propyl)-deca(dimethylsiloxane) (ED10E),1,3(bis-3-(4-hydroxy-3-methoxy)-propyl)-1,1,3,3,-tetramethyl disiloxane(EMME), or oligomers of similar structure. As these are also hydroxyterminated, they may also be introduced into the chain by reaction withthe dicarboxylic acid dichloride. Examples of siloxane oligomers used inthe invention comprise Formula XII,

wherein q is in one embodiment 1–99, and in another embodiment 30–70. Inone particular embodiment q has a value of 1–20. In another particularembodiment q has a value of 10–20.

Examples of siloxane oligomers used in the invention also compriseFormula XVI, wherein the moiety Ar is derived from adihydroxy-substituted aromatic hydrocarbon and x has a value of about 10to about 100:

In another embodiment, bisphenol A functionalized with a long chainester may be incorporated into the RP-co-PC by replacing part of the BPAnormally used with ester-bisphenol. In an embodiment, the esterbisphenol comprises compounds such as the compounds of Formula XIII,

where R¹⁶ is alkyl chain comprising 4 to at least 20 carbons. In anembodiment, incorporation of ester-bisphenol may reduce Tg, as well asincreasing flow and reducing flow energy. In some cases, however, theresultant polymer may be yellow after processing. Purification of theester diphenol may alleviate the color problem.

In yet another embodiment, soft-block esters are introduced into anRP-co-PC copolymer as esters by co-reaction of aliphatic diacidchlorides along with the iso/terephthaloyl chloride. In an embodiment,incorporation of these long-chain aliphatic groups results in a dramaticdrop in viscosity and Tg.

The method further comprises combining at least one catalyst with theinterfacial reaction mixture. The catalyst may be present in variousembodiments at a total level of 0.1 to 10 mole %, and in someembodiments at a total level of 0.2 to 6 mole % based on total molaramount of acid chloride groups. Suitable catalysts for the interfacialreaction comprise tertiary amines, quaternary ammonium salts, quaternaryphosphonium salts, hexaalkylguanidinium salts, and mixtures thereof.

Suitable tertiary amines include triethylamine, dimethylbutylamine,diisopropylethylamine, 2,2,6,6-tetramethylpiperidine, and mixturesthereof. Other contemplated tertiary amines includeN—C₁–C₆-alkyl-pyrrolidines, such as N-ethylpyrrolidine,N—C₁–C₆-piperidines, such as N-ethylpiperidine, N-methylpiperidine, andN-isopropylpiperidine, N—C₁–C₆-morpholines, such as N-ethylmorpholineand N-isopropyl-morpholine, N—C₁–C₆-dihydroindoles,N—C₁–C₆-dihydroisoindoles, N—C₁–C₆-tetrahydroquinolines,N—C₁–C₆-tetrahydroisoquinolines, N—C₁–C₆-benzo-morpholines,1-azabicyclo-[3.3.0]-octane, quinuclidine,N—C₁–C₆-alkyl-2-azabicyclo-[2.2.1]-octanes,N—C₁–C₆-alkyl-2-azabicyclo-[3.3.1]-nonanes, andN—C₁–C₆-alkyl-3-azabicyclo-[3.3.1]-nonanes,N,N,N′,N′-tetraalkylalkylene-diamines, includingN,N,N′,N′-tetraethyl-1,6-hexanediamine. In various embodiments tertiaryamines are triethylamine and N-ethylpiperidine. Also included are4-dimethylaminopyridine, 4-pyrrolidino pyridine and other4-dialkylaminopyridines.

When the catalyst consists of at least one tertiary amine alone, thenthe catalyst may be present in one embodiment at a total level of 0.1 to10 mole %, in another embodiment at a total level of 0.2 to 6 mole %, inanother embodiment at a total level of 1 to 4 mole %, and in stillanother embodiment at a total level of 2.5 to 4 mole % based on totalmolar amount of acid chloride groups. In one embodiment of theinvention, all of the tertiary amine is present at the beginning of thereaction before addition of dicarboxylic acid dichloride to resorcinolmoiety. In another embodiment a portion of any tertiary amine is presentat the beginning of the reaction and a portion is added following orduring addition of dicarboxylic acid dichloride to resorcinol moiety. Inthis latter embodiment the amount of any tertiary amine initiallypresent with resorcinol moiety may range in one embodiment from about0.005 wt. % to about 10 wt. %, in another embodiment from about 0.01 toabout 5 wt. %, and in still another embodiment from about 0.02 to about3 wt. % based on total amine.

Suitable quaternary ammonium salts, quaternary phosphonium salts, andhexaalkylguanidinium salts include halide salts such astetraethylammonium bromide, tetraethylammonium chloride,tetrapropylammonium bromide, tetrapropylammonium chloride,tetrabutylammonium bromide, tetrabutylammonium chloride,methyltributylammonium chloride, benzyltributylammonium chloride,benzyltriethylammonium chloride, benzyltrimethylammonium chloride,trioctylmethylammonium chloride, cetyldimethylbenzylammonium chloride,octyltriethylammonium bromide, decyltriethylammonium bromide,lauryltriethylammonium bromide, cetyltrimethylammonium bromide,cetyltriethylammonium bromide, N-laurylpyridinium chloride,N-laurylpyridinium bromide, N-heptylpyridinium bromide,tricaprylylmethylammonium chloride (sometimes known as ALIQUAT 336),methyltri-C₈–C₁₀-alkyl-ammonium chloride (sometimes known as ADOGEN464), N,N,N′,N′,N′-pentaalkyl-alpha, omega-amine-ammonium salts such asdisclosed in U.S. Pat. No. 5,821,322; tetrabutylphosphonium bromide,benzyltriphenylphosphonium chloride, triethyloctadecylphosphoniumbromide, tetraphenylphosphonium bromide, triphenylmethylphosphoniumbromide, trioctylethylphosphonium bromide, cetyltriethylphosphoniumbromide, hexaalkylguanidinium halides, hexaethylguanidinium chloride,and the like, and mixtures thereof. Also included are hydroxides such asmethyltributylammonium hydroxide.

Organic solvents substantially immiscible with water include those whichin one embodiment are less than about 5 wt. %, and in another embodimentless than about 2 wt. % soluble in water under the reaction conditions.Suitable organic solvents include dichloromethane, trichloroethylene,tetrachloroethane, chloroform, 1,2-dichloroethane, toluene, xylene,trimethylbenzene, chlorobenzene, o-dichlorobenzene, and mixturesthereof. In a particular embodiment the solvent is dichloromethane.

For the first step (generation of resorcinol arylate polyester) the pHof the reaction mixture is maintained in some embodiments between about3 and about 8.5, and in other embodiments between about 5 and about 8,throughout addition of the at least one dicarboxylic acid dichloride tothe at least one resorcinol moiety. For the second step, the preferredpH range is 9.5–11.

Suitable reagents to maintain the pH include alkali metal hydroxides,alkaline earth hydroxides, and alkaline earth oxides. In someembodiments the reagents are potassium hydroxide and sodium hydroxide.In a particular embodiment the reagent is sodium hydroxide. The reagentto maintain pH may be included in the reaction mixture in any convenientform. In some embodiments said reagent is added to the reaction mixtureas an aqueous solution simultaneously with the at least one dicarboxylicacid dichloride.

The temperature of the reaction mixture may be any convenienttemperature that provides a rapid reaction rate and a resorcinolarylate-containing polymer substantially free of anhydride linkages.Convenient temperatures include those from about −20° C. to the boilingpoint of the water-organic solvent mixture under the reactionconditions. In one embodiment the reaction is performed at the boilingpoint of the organic solvent in the water-organic solvent mixture. Inanother embodiment the reaction is performed at the boiling point ofdichloromethane.

Preferably, the total molar amount of acid chloride groups added to thereaction mixture is stoichiometrically deficient relative to the totalmolar amount of phenolic groups. This stoichiometric ratio is desirableso that hydrolysis of acid chloride groups is minimized, and so thatnucleophiles such as phenolic and/or phenoxide may be present to destroyany adventitious anhydride linkages, should any form under the reactionconditions. The total molar amount of acid chloride groups includes theat least one dicarboxylic acid dichloride, and any mono-carboxylic acidchloride chain-stoppers and any tri- or tetra-carboxylic acid tri- ortetra-chloride branching agents which may be used. The total molaramount of phenolic groups includes resorcinol moieties, and anymono-phenolic chain-stoppers and any tri- or tetra-phenolic branchingagents which may be used. The stoichiometric ratio of total phenolicgroups to total acid chloride groups is in one embodiment about 1.5–1.01to 1 and in another embodiment about 1.2–1.02 to 1.

In an embodiment, at least one chain-stopper (also referred to sometimeshereinafter as capping agent) may be present in the methods andcompositions of the present invention. A purpose of adding at least onechain-stopper is to limit the molecular weight, thus providing polymerwith controlled molecular weight and favorable processability. Achain-stopper may be at least one of mono-phenolic compounds,mono-carboxylic acid chlorides, and/or mono-chloroformates.

For example, mono-phenolic compounds suitable as chain stoppers includemonocyclic phenols, such as phenol, C₁–C₂₂ alkyl-substituted phenols,p-cumyl-phenol, p-tertiary-butyl phenol, hydroxy diphenyl; monoethers ofdiphenols, such as p-methoxyphenol. Alkyl-substituted phenols includethose with branched chain alkyl substituents having 8 to 9 carbon atoms,preferably in which about 47 to 89% of the hydrogen atoms are part ofmethyl groups as described in U.S. Pat. No. 4,334,053. For someembodiments a mono-phenolic UV absorber is used as capping agent. Suchcompounds include 4-substituted-2-hydroxybenzophenones and theirderivatives, aryl salicylates, monoesters of diphenols, such asresorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and theirderivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives,and like compounds. In some embodiments mono-phenolic chain-stoppers arephenol, p-cumylphenol, and/or resorcinol monobenzoate.

Mono-carboxylic acid chlorides suitable as chain stoppers includemonocyclic, mono-carboxylic acid chlorides, such as benzoyl chloride,C₁–C₂₂ alkyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and mixtures thereof, polycyclic,mono-carboxylic acid chlorides, such as trimellitic anhydride chloride,and naphthoyl chloride; and mixtures of monocyclic and polycyclicmono-carboxylic acid chlorides. The chlorides of aliphaticmonocarboxylic acids with up to 22 carbon atoms are also suitable.Functionalized chlorides of aliphatic monocarboxylic acids, such asacryloyl chloride and methacryoyl chloride, are also suitable. Suitablemono-chloroformates include monocyclic, mono-chloroformates, such asphenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate, toluene chloroformate, and mixtures thereof.

In another embodiment, the invention may encompass the inclusion of atleast one branching agent such as a trifunctional or higher functionalcarboxylic acid chloride and/or trifunctional or higher functionalphenol. Such branching agents, if included, can typically be used inquantities of 0.005 to 1 mole %, based on dicarboxylic acid dichloridesor resorcinol moieties used, respectively. Suitable branching agentsinclude, for example, trifunctional or higher carboxylic acid chlorides,such as trimesic acid trichloride, cyanuric acid trichloride,3,3′,4,4′-benzophenone tetracarboxylic acid tetrachloride,1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromelliticacid tetrachloride, and trifunctional or higher phenols, such asphloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenyl methane,2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane,2,4-bis-(4-hydroxyphenylisopropyl)-phenol,tetra-(4-hydroxyphenyl)-methane,2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methyl phenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,tetra-(4-[4-hydroxyphenylisopropyl]-phenoxy)-methane,1,4-bis-[(4,4-dihydroxytriphenyl)methyl]-benzene. Phenolic branchingagents may be introduced first with the resorcinol moieties while acidchloride branching agents may be introduced together with aciddichlorides.

Polymer Blends

The polymers and copolymers comprising thermally stable resorcinolarylate polyester chain members may be employed in blends with at leastone other polymer, especially polycarbonates (hereinafter sometimesdesignated “PC”), polyesters, copolyestercarbonates, polyarylates,polyetherimides, polyphenylene ethers, and addition polymers. Relatedblends are disclosed in commonly owned U.S. Pat. No. 6,143,839. Forexample, such blends may be used for injection molding.

The polycarbonates in the blend compositions of the invention are, forthe most part, similar in molecular structure to the carbonate blocks ofthe block copolyestercarbonate as described hereinabove, withbisphenol-A homo- and copolycarbonates generally being preferred in someembodiments. Polyesters are illustrated by poly(alkylenedicarboxylates), especially poly(ethylene terephthalate) (hereinaftersometimes designated “PET”), poly(1,4-butylene terephthalate)(hereinafter sometimes designated “PBT”), poly(trimethyleneterephthalate) (hereinafter sometimes designated “PTT”), poly(ethylenenaphthalate) (hereinafter sometimes designated “PEN”), poly(butylenenaphthalate) (hereinafter sometimes designated “PBN”),poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate) (hereinaftersometimes designated “PETG”), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate) (hereinaftersometimes designated “PCCD”), and especially poly(alkylenearenedioates), with poly(ethylene terephthalate) and poly(1,4-butyleneterephthalate) being preferred in some embodiments.

Multilayer Articles

The thermostable, weatherable polymers of the present invention may beapplied to substrates to provide protection against UV induceddegradation. Thus, in another embodiment, the present inventioncomprises multilayer articles comprising a substrate layer and least onecoating layer thereon, said coating layer comprising at least onepolymer comprising structural units derived from at least one1,3-dihydroxybenzene moiety, at least one aromatic dicarboxylic acidmoiety, at least one bisphenol moiety, and at least one soft-blockmoiety and prepared by methods embodied in the present invention.

In the present context a multilayer article is one containing at leasttwo layers. In an embodiment, the substrate comprises at least onethermoplastic polymer, a thermoset polymer, a cellulosic material,glass, ceramic, or metal. Optionally, the multilayer articles mayfurther comprise an interlayer, for example an adhesive interlayer,between any substrate layer and any thermally stable polymer coatinglayer.

Multilayer articles of the invention include, but are not limited to,those which comprise a substrate layer and a coating layer of saidthermally stable polymer; those which comprise a substrate layer with acoating layer of said thermally stable polymer on each side of saidsubstrate layer; and those which comprise a substrate layer and at leastone coating layer of said thermally stable polymer with at least oneinterlayer between a substrate layer and a coating layer. Any interlayermay be transparent, translucent, or opaque, and/or may contain anadditive, for example a colorant or decorative material such as metalflake. If desired, an overlayer may be included over the coating layerof thermally stable polymer, for example to provide abrasion or scratchresistance. The substrate layer, coating layer of thermally stablepolymer, and any interlayers or overcoating layers are often incontiguous superposed contact with one another.

Within the context of the present invention, it should be understoodthat any coating layer comprising a thermally stable polymer comprisingRP-co-PC/soft-block members may also include polymer comprisingo-hydroxy-benzophenone or analogous chain members resulting from Friesrearrangement of said resorcinol arylate chain members, for exampleafter exposure of said coating layer to UV-light. Typically, apreponderance of any polymer comprising o-hydroxy-benzophenone oranalogous chain members will be on that side or sides of said coatinglayer exposed to UV-light and will overlay in a contiguous superposedlayer or layers that polymer comprising unrearranged resorcinol arylatechain members. If the exposed layer is worn away or otherwise removed,polymer comprising o-hydroxybenzophenone or analogous chain members iscapable of regenerating or renewing itself from the resorcinolarylate-containing layer or layers, thus providing continuous protectionfor any UV-light sensitive layers.

In an embodiment, the coating of the present invention my furthercomprise a stabilizer additive. Such additives may have a beneficialeffect on color despite the fact that polymers comprising resorcinolarylate polyester chain members and their Fries rearrangement productsthemselves protect against photoyellowing. In the present context astabilizer additive is an additive which provides one or both of lowerinitial color or additional resistance to weathering, as measured forexample by initial yellowness index (YI), or by resistance to yellowingand change in color, when compared to a similar coating without at leastone stabilizer additive. In a particular embodiment the stabilizeradditive comprises at least one auxiliary color stabilizer additive. Inanother particular embodiment the stabilizer additive comprises at leastone auxiliary light stabilizer additive. In one embodiment the presenceof at least one auxiliary UV absorber as stabilizer additive providesadditional resistance to weathering, for example as measured by initialyellowness index (YI), or resistance to yellowing and change in color,when compared to a similar coating without at least one auxiliary UVabsorber. Since resorcinol arylate-comprising polymers generate UVabsorber in situ, it is unexpected that the addition of auxiliary UVabsorber would affect the amount of color or yellowness generated.

The material of the substrate layer in the articles of this inventionmay include at least one thermoplastic polymer as described in commonlyowned U.S. Pat. No. 6,306,507. Thermoplastic polymers include, but arenot limited to, polycarbonates, particularly aromatic polycarbonates,polyacetals, polyarylene ethers, polyphenylene ethers, polyarylenesulfides, polyphenylene sulfides, polyimides, polyamideimides,polyetherimides, polyetherketones, polyaryletherketones,polyetheretherketones, polyetherketoneketones, polyamides, polyesters,liquid crystalline polyesters, polyetheresters, polyetheramides,polyesteramides, and polyestercarbonates (other than those employed forthe coating layer, as defined hereinafter). In some embodimentspolycarbonates and polyesters are preferred. A substrate layer mayadditionally contain art-recognized additives including, but not limitedto, colorants, pigments, dyes, impact modifiers, stabilizers, colorstabilizers, heat stabilizers, UV screeners, UV absorbers, flameretardants, fillers, flow aids, ester interchange inhibitors, and moldrelease agents.

Suitable polycarbonate substrates include homopolycarbonates comprisingstructural units of the type described for the organic carbonate blocksin the copolyestercarbonates of the invention. In some embodiments thepolycarbonates are bisphenol A homo- and copolycarbonates. In variousembodiments the weight average molecular weight of the initialpolycarbonate ranges from about 5,000 to about 100,000; in otherembodiments the weight average molecular weight of the initialpolycarbonate ranges from about 25,000 to about 65,000.

The polycarbonate substrate may also be a copolyestercarbonate (otherthan that copolyestercarbonate employed for the coating layer as definedhereinafter). Such copolymers typically comprise, in addition to theorganic carbonate units, ester units such as isophthalate and/orterephthalate. The copolyestercarbonates which find use as substrates inthe instant invention and the methods for their preparation are wellknown in the art as disclosed in, for example, U.S. Pat. Nos. 3,030,331;3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,238,596; 4,238,597;4,487,896; and 4,506,065.

Polyester substrates include, but are not limited to, poly(alkylenedicarboxylates), especially poly(ethylene terephthalate),poly(1,4-butylene terephthalate), poly(trimethylene terephthalate),poly(ethylene naphthalate), poly(butylene naphthalate),poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate). Alsoincluded are polyarylates as described hereinabove, illustrativeexamples of which include those comprising structural units derived frombisphenol A, terephthalic acid, and isophthalic acid.

Additional polymer substrates include homo- and copolymeric aliphaticolefin and functionalized olefin polymers (which are homopolymers andcopolymers comprising structural units derived from aliphatic olefins orfunctionalized olefins or both), and their alloys or blends.Illustrative examples include, but are not limited to, polyethylene,polypropylene, thermoplastic polyolefin (“TPO”), ethylene-propylenecopolymer, poly(vinyl chloride), poly(vinyl chloride-co-vinylidenechloride), poly(vinyl fluoride), poly(vinylidene fluoride), poly(vinylacetate), poly(vinyl alcohol), poly(vinyl butyral), poly(acrylonitrile),acrylic polymers such as those of (meth)acrylamides or of alkyl(meth)acrylates such as poly(methyl methacrylate) (“PMMA”), and polymersof alkenylaromatic compounds such as polystyrenes, includingsyndiotactic polystyrene. In some embodiments the preferred additionpolymers are polystyrenes and especially the so-called ABS and ASAcopolymers, which may contain thermoplastic, non-elastomericstyrene-acrylonitrile side chains grafted on an elastomeric base polymerof butadiene and alkyl acrylate, respectively.

Blends of any of the foregoing polymers may also be employed assubstrates. Typical blends include, but are not limited to, thosecomprising PC/ABS, PC/ASA, PC/PBT, PC/PET, PC/polyetherimide,PC/polysulfone, polyester/polyetherimide, PMMA/acrylic rubber,polyphenylene ether-polystyrene, polyphenylene ether-polyamide orpolyphenylene ether-polyester. Although the substrate layer mayincorporate other thermoplastic polymers, the above-describedpolycarbonates and/or addition polymers often constitute the majorproportion thereof.

The substrate layer in the multilayer articles of this invention mayalso comprise at least one of any thermoset polymer. Suitable thermosetpolymer substrates include, but are not limited to, those derived fromepoxys, cyanate esters, unsaturated polyesters, diallylphthalate,acrylics, alkyds, phenol-formaldehyde, novolacs, resoles, bismaleimides,PMR resins, melamine-formaldehyde, urea-formaldehyde, benzocyclobutanes,hydroxymethylfurans, and isocyanates. In one embodiment of the inventionthe thermoset polymer substrate comprises a RIM material. In anotherembodiment of the invention the thermoset polymer substrate furthercomprises at least one thermoplastic polymer, such as, but not limitedto, polyphenylene ether, polyphenylene sulfide, polysulfone,polyetherimide, or polyester. Said thermoplastic polymer is typicallycombined with thermoset monomer mixture before curing of said thermoset.

In one embodiment of the invention a thermoplastic or thermosetsubstrate layer also incorporates at least one filler and/or pigment.Illustrative extending and reinforcing fillers, and pigments includesilicates, zeolites, titanium dioxide, stone powder, glass fibers orspheres, carbon fibers, carbon black, graphite, calcium carbonate, talc,mica, lithopone, zinc oxide, zirconium silicate, iron oxides,diatomaceous earth, calcium carbonate, magnesium oxide, chromic oxide,zirconium oxide, aluminum oxide, crushed quartz, calcined clay, talc,kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetictextile fibers, especially reinforcing fillers such as glass fibers,carbon fibers, and metal fibers, as well as colorants such as metalflakes, glass flakes and beads, ceramic particles, other polymerparticles, dyes and pigments which may be organic, inorganic ororganometallic. In another embodiment the invention encompassesmultilayer articles comprising a filled thermoset substrate layer suchas a sheet-molding compound (SMC).

The substrate layer may also comprise at least one cellulosic materialincluding, but not limited to, wood, paper, cardboard, fiber board,particle board, plywood, construction paper, Kraft paper, cellulosenitrate, cellulose acetate butyrate, and like cellulosic-containingmaterials. The invention also encompasses blends of at least onecellulosic material and either at least one thermoset polymer(particularly an adhesive thermoset polymer), or at least onethermoplastic polymer (particularly a recycled thermoplastic polymer,such as PET or polycarbonate), or a mixture of at least one thermosetpolymer and at least one thermoplastic polymer.

Multilayer articles encompassed by the invention also include thosecomprising at least one glass layer. Typically any glass layer is asubstrate layer, although multilayer articles comprising a thermallystable polymer coating layer interposed between a glass layer and asubstrate layer are also contemplated. Depending upon the nature ofcoating and glass layers, at least one adhesive interlayer may bebeneficially employed between any glass layer and any thermally stablepolymer coating layer. The adhesive interlayer may be transparent,opaque or translucent. For many applications it is preferred that theinterlayer be optically transparent in nature and generally have atransmission of greater than about 60% and a haze value less than about3% with no objectionable color.

Metal articles exposed to UV-light may exhibit tarnishing and otherdetrimental phenomena. In another embodiment the invention encompassesmultilayer articles comprising at least one metal layer as substratelayer. Representative metal substrates include those comprising brass,aluminum, magnesium, chrome, iron, steel, copper, and other metals oralloys or articles containing them, which may require protection fromUV-light or other weather phenomena. Depending upon the nature ofcoating and metal layers, at least one adhesive interlayer may bebeneficially employed between any metal layer and any thermally stablepolymer coating layer.

It is also within the scope of the invention for other polymers to bepresent which are miscible in at least some proportions with the coatinglayer of the present invention. Illustrative examples of at leastpartially miscible polymers include polyetherimide and polyesters suchas PBT, PET, PTT, PEN, PBN, PETG, PCCD, and bisphenol A polyarylate. Inone embodiment the coating layer polymer consists essentially ofthermally stable resorcinol arylate polyesters, copolyesters, orcopolyestercarbonates.

In one embodiment, application of the at least one coating layer may beperformed by solvent-casting. In another embodiment application of saidcoating layer comprises fabrication of a separate sheet thereof followedby application to the second layer, or by simultaneous production ofboth layers, typically in a melt process. Thus, there may be employedsuch methods as thermoforming, compression molding, co-injectionmolding, coextrusion, overmolding, blow molding, multi-shot injectionmolding and placement of a film of the coating layer material on thesurface of the second layer followed by adhesion of the two layers,typically in an injection molding apparatus; e.g., in-mold decoration,or in a hot-press. These operations may be conducted underart-recognized conditions.

The articles of this invention are typically characterized by the usualbeneficial properties of the substrate layer, in addition toweatherability as may be evidenced by such properties as improvedinitial gloss, improved initial color, improved resistance toultraviolet radiation and maintenance of gloss, improved impactstrength, and resistance to organic solvents encountered in their finalapplications. Depending upon such factors as the coating layer/substratecombination, the multilayer articles may possess recycling capability,which makes it possible to employ the regrind material as a substratefor further production of articles of the invention.

Copolymer compositions that are substantially transparent and methods offorming these copolymer compositions are disclosed herein. Suchcopolymer compositions comprise arylate polyester units, aromaticcarbonate units, and soft block moieties. General types of arylatepolyester units for use in these compositions are those having Formula(XVII):

wherein D¹ is the reaction residue of a dihydroxy aromatic compound, andwherein the polymer chain carboxyl groups on the aromatic acid radicalmay be distributed ortho-, meta-, or para- to one another on thearomatic ring. The term “reaction” where used in conjunction with adihydroxy compound or dihydroxy aromatic compound may comprise thecondensation product of these with a carbonyl group, functionalizedsilicon group, and the like. Specifically, where used in describing D¹,the term “reaction residue” refers to the organic radical portion of thedihydroxy aromatic compound, exclusive of terminal oxygen radicals ofthe hydroxy groups, which derives from the aforementioned condensation.Further, the aromatic acid radical may be a combination of one or moreof the ortho-, meta-, or para-disubstituted forms. In one embodiment, D¹is the reaction residue of a bisphenol of Formula V or Formula VIII, forexample 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,bisphenol A, 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane, or a combination comprising atleast one of the foregoing bisphenols.

In another embodiment, D¹ is the reaction residue of a resorcinol ofFormula I, and the arylate polyester unit is a resorcinol arylatepolyester unit of Formula III. Specifically, in this embodiment, D¹ isthe reaction residue of resorcinol, 2-methyl resorcinol, and the like.Combinations comprising at least one of the foregoing resorcinolcompounds may also be used. In a further embodiment, D¹ is a combinationof a bisphenol and a resorcinol. The ratio of resorcinol to bisphenolmay be 1:99 to 99:1.

Where a soft block moiety comprises a polysiloxane unit, suitablepolysiloxane units comprise repeating diorganosiloxane units of Formula(XVIII):

wherein each occurrence of R³ may be the same or different and isindependently a C₁₋₁₂ hydrocarbyl. The diorganosiloxane units aregenerally present in the form of blocks containing 1 to 1000 units,specifically 10 to 100, more specifically 15 to 75, and mostspecifically 20 to 60. As is readily understood by one of ordinary skillin the art, the number of diorganosiloxane units represents an averagevalue.

A specific type of suitable polysiloxane unit comprises Formula (XIX):

wherein R³ is as described above, x is 1 to 1000, each occurrence of R⁴is independently a divalent C₁–C₃₀ hydrocarbylene, and wherein thepolymerized polysiloxane unit is the reaction residue of itscorresponding dihydroxy compound. In one embodiment, each occurrence ofR⁴ independently is of Formula (XX):

wherein each occurrence of R⁶ is independently H or C₁–C₁₂ hydrocarbyl.Each R⁵ in Formula (XX) may be the same or different, and may be ahalogen, cyano, nitro, C₁–C₈ alkylthio, C₁–C₈ alkyl, C₁–C₈ alkoxy, C₂–C₈alkenyl, C₂–C₈ alkenyloxy group, C₃–C₈ cycloalkyl, C₃–C₈ cycloalkoxy,C₆–C₁₀ aryl, C₆–C₁₀ aryloxy, C₇–C₁₂ aralkyl, C₇–C₁₂ aralkoxy, C₇–C₁₂alkaryl, or C₇–C₁₂ alkaryloxy, and b is 1 to 8. Each a is independently0, 1, 2, 3, or 4. In one embodiment, the aryl end has connectivity to anoxygen atom, and the alkyl end has connectivity to a silicon atom. Inanother embodiment, the oxygen substituent may be disposed ortho, meta,or para to the —C(R⁶)₂)— group.

The polysiloxane units may comprise repeatable structural units of theFormula (XXI):

wherein R³ and R⁵ are as described for Formulas XIX and XX above, q is 1to 1000, R⁷ is a divalent organic radical disposed in the para positionrelative to the backbone oxygen, and wherein the polymerized unit is thereaction residue of its corresponding dihydroxy compound. For example,R⁷ may be a C₁–C₁₃ alkylene, C₁–C₁₃ alkyleneoxy, C₂–C₁₃ alkenyl, C₂–C₁₃alkenyloxy, C₃–C₆ cycloalkylene, C₃–C₆ cycloalkleneoxy, C₆–C₁₀ arylene,C₆–C₁₀ aryleneoxy, C₇–C₁₃ aralkylene, C₇–C₁₃ aralkylenoxy, C₇–C₁₃alkarylene, or C₇–C₁₃ alkaryleneoxy. Combinations of the foregoing R⁷groups may be used in the same copolymer. In one embodiment, each R³ inFormula (XXI) may be the same or different, and is C₁₋₈ alkyl and C₆₋₁₃aryl; a is 1; each R⁵ is a C₁₋₃ alkoxy; and each R⁷ is a C₁–C₁₃alkylene. In another specific embodiment, each R³ is a C₁–C₃ alkyl; eachR⁵ is a C₁–C₃ alkoxy or a C₁–C₃ alkyl; a is 1; and each R⁷ is adimethylene, trimethylene or tetramethylene. In another embodiment, eachR³ is methyl, each R⁵ is methoxy, a is 1, and each R⁷is a divalent C₁–C₃aliphatic group. In a more specific embodiment, q is 1 to 99, R³ ismethyl, each R⁵ is methoxy, a is 1, each R⁷ is a trimethylene group, R⁷and R⁵ are substituted meta to each other, and R⁵ is substituted orthoto the oxygen radical. Such units may be derived from hydroxyarylterminated polysiloxanes of Formula XII.

The polysiloxane units may be repeatable structural units of FormulaXXII:

wherein x is 1 to 1000 and D¹ is as defined above. In this Formula, thepolysiloxane unit is connected through an oxygen linkage to an endgroup, wherein each end group is independently the reaction residue of adihydroxy compound of the Formula HO-D¹-OH. In one embodiment, thedihydroxy compound is a dihydroxy aromatic compound of Formula VIII. Ina specific embodiment, each R³ is methyl, x is 1 to 100, and D¹ is anaromatic group and may be represented by Ar as defined above. Such unitsmay be derived from hydroxyaryl terminated polysiloxanes of Formula XVI.

Hydroxyaryl-terminated polysiloxanes can be made by effecting a platinumcatalyzed addition between an aliphatically unsaturated monohydricphenol and a siloxane of the Formula XXIII,

wherein R³ is as previously defined, D is 1 to 1000, and Z is H. Some ofthe aliphatically unsaturated monohydric phenols that can be used tomake hydroxyaryl-terminated poly(diorganosiloxane)s are, for example,4-allyl phenol, 4-allyl-2-methoxy phenol (eugenol), 2-alkylphenol,4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol,4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol,2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol,2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol,2-allyl-4,6-dimethylphenol, and the like.

Hydroxyaryl-terminated polysiloxanes can also be prepared by thecondensation of hydride-terminated polysiloxane XXIII, wherein Z is H,with a halomethyl- or sulfonatomethylene-substituted aromatic compoundin the presence of a base or copper catalyst, followed by the removal ofany hydroxyl protecting group used, such as acetate or trimethylsilyl.Suitable halomethyl- or sulfonatomethylene-substituted aromaticcompounds of this type include 4-acetoxybenzyl chloride,4-trimethylsilylbenzyl chloride, 4-methoxymethyloxybenzyl chloride,4-acetoxybenzyl toluenesulfonate, 4 trimethylsilylbenzyltoluenesulfonate, and the like.

Hydroxyaryl-terminated polysiloxanes can also be prepared by thecondensation of: polysiloxane XXIII, wherein Z is acetoxy or halogen,specifically Cl, with a dihydroxy aromatic compound of Formula VIII,optionally in the presence of a base or other catalyst. Specificsuitable dihydroxy compounds for this purpose include, but are notlimited to, 1,1-bis(4-hydroxyphenyl) methane,1,1-bis(4-hydroxyphenyl)ethane, bisphenol A,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane, and1,1-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising atleast one of the foregoing dihydroxy compounds may also be used.

A copolymer composition comprises an arylate polyester unit, an aromaticcarbonate unit, and a soft block moiety. The copolymer composition maycomprise 2 to 98 mole percent (mol-%), specifically 5 to 95 mol-%, andmore specifically 8 to 92 mol-% of the arylate polyester unit; 2 to 98mol-%, specifically 5 to 95 mol-%, and more specifically 8 to 92 mol-%of the aromatic carbonate unit; and less than or equal to 5 mol-%,specifically less than or equal to 3 mol-%, and more specifically lessthan or equal to 1 mol-% of the soft block moiety, and wherein the softblock moiety is present in an amount greater than 0.01 mol-%. In oneembodiment, the soft block moiety is a polysiloxane unit comprisingFormula XVIII.

In addition, where the soft block moiety is a polysiloxane unitcomprising diorganosiloxane units of Formula XVIII, the polysiloxaneunit may be present in the copolymer composition from 0.1 to 75 weightpercent (wt %), specifically from 0.5 wt % to 20 wt %, and morespecifically from 0.75 wt % to 15 wt % of the total weight of thecopolymer composition.

Individual occurences of the soft-block moiety are substantially linkedto each other by at least one spacer unit, wherein a spacer unitcomprises one or more arylate polyester units, one or more aromaticcarbonate units, or a combination of each of these. The term“substantially linked”, as used herein, means that greater than or equalto 90 mol-%, specifically greater than or equal to 95 mol-%, morespecifically greater than or equal to 99 mol-%, and most specificallygreater than or equal to 99.5 mol-% of the soft block moieties arelinked by a spacer unit as defined above.

In an embodiment, a soft block moiety is a polysiloxane unit comprisingdiorganosiloxane units of Formula XVIII, and a spacer unit is one ormore resorcinol arylate polyester units, one or more bisphenol polyesterunits, one or more aromatic carbonate units, or a combination of two ormore of each of these.

Soft block moieties may be randomly distributed within the polymerchain. As used herein, “randomly distributed” means that any twooccurrences of a soft block moiety are linked to each other by a randomnumber of spacer units. Specifically, occurrences of the soft blockmoiety may be substantially randomly distributed within the polymerchain. As used herein, “substantially randomly distributed” means thatgreater than or equal to 95 mol-%, specifically greater than or equal to99 mol-%, or most specifically greater than or equal to 99.5 mol % ofoccurrences of a soft block moiety are randomly distributed asdetermined by proton nuclear magnetic resonance (NMR) spectroscopy.

The copolymer composition has a light transmission greater than or equalto 55%, specifically greater than or equal to 60% and more specificallygreater than or equal to 70%, as determined according to ASTM D1003-00.The copolymer may also have a haze less than or equal to 30%, preferablyless than or equal to 25%, and most specifically less than or equal to20% as determined according to ASTM D1003-00. Without being bound bytheory, where the soft block moiety is a polysiloxane unit, it isbelieved that on a molecular scale both the transparency and haze of acopolymer composition comprising polysiloxane units are each related tothe number of polysiloxane units within the polymer chain, the averagesize of the polysiloxane unit (as defined by the number of repeatingdiorganosiloxane subunits of Formula XVIII), the randomness of thedistribution of the polysiloxane units in the polymer chain, or acombination of one or more of these factors. It is believed that a morerandom distribution of polysiloxane units within a copolymer providesboth a greater degree of transparency and a lesser degree of haze.Reaction conditions, relative amounts of starting materials, and/ortypes of starting materials may therefore be selected so as to adjustthe distribution of the polysiloxane units, and thus the transparencyand haze of the composition.

Polysiloxane units dispersed non-randomly in a copolymer composition mayself-aggregate into polysiloxane-containing regions within the copolymercomposition, absent a mechanism to prevent, minimize, or mitigate theiraggregation. The difference in refractive indices between regions ofpolysiloxane units, and the surrounding regions comprising aromaticpolyesters or polycarbonates, can lead to substantial scattering ofincident light wherein sufficient numbers of polysiloxane regions ofsufficient size are present. This may lead at least to the presence ofhaze, at most the opacity of the copolymer, and correspondingly at leastto a diminished light transmission through a film comprising thecopolymer. Minimizing the formation of regions of polysiloxane unitsduring the reaction to form a copolymer may therefore lead to increasedtransparency and lower haze in copolymer compositions comprisingpolysiloxanes.

A cause of non-random distribution of units in a copolymer may beattributed to different reactivities of polymerizable units present inthe polymerization reaction. Dihydroxy compounds comprising soft blockmoieties, specifically where soft block moieties comprising polysiloxaneunits of general structures XIX and XXII, are believed to have a lowerreactivity toward phosgenation and subsequent reaction with dihydroxycompounds, than a dihydroxy compounds comprising an arylate polyesterunit or a dihydroxy compound of Formula VIII. More specifically,polysiloxane units having endgroups of general structures XX may havesubstituent groups R⁵ disposed ortho to the oxygen radical whichprovides backbone connectivity. One skilled in the art will appreciatethat a substituent group subsitituted ortho to a reactive site providesa steric barrier and may decrease reactivity of the reactive site. Otherfactors affecting the reactivity includes multiple substituents, forexample, in Formula XX, wherein a is greater than 1; the size of the R⁵subsitituent, wherein a larger substituent decreases reactivity further;electronic effects such as deactivating substituents such as carboxylategroups or activating substituents such as hydroxyl groups; and theintramolecular structure of the polysiloxane unit. Another factoraffecting the reactivity of a reactive site is the nature of thereactive site, wherein a polar reactive site such as, for example, ahydroxyl group, may hydrogen bond to another hydroxyl group in an inter-or intramolecular interaction, and further decrease the reactivity ofthe group. It will be further appreciated that reference to a reactivesite or reactive group refers to the portion of the polysiloxane unitwhich participates in the formation of a carbonate or ester bond in apolymerization reaction. An effect of this lower reactivity may be theformation of non-uniformly distributed soft block moieties in thepolymer chain, where the soft block moieties are not substantiallyseparated. By adjusting the reactivity of the reactants in thepolymerization reaction, a more random distribution may be effected.

One method of forming randomly distributed soft block moieties incopolymer compositions during the polymerization reaction is to providecopolymerizable reactants which have substantially the same reactivitytoward each other. This may be accomplished by pre-reacting all of thepolymerizable units, including the least reactive unit, with a reactivecomponent of polymerization reaction, to form separate units with asubstantially equivalent degree of reactivity. In an embodiment, both adihydroxy aromatic compound comprising arylate polyester units ofFormula XVII and a dihydroxy aromatic compound comprising Formula VIIIare each believed to have higher reactivities than a soft block moietycomprising a dihydroxy aromatic compound comprising a polysiloxane unitof Formula XXI, when subject to carbonylation reaction conditions toform a polycarbonate. A method of imparting each of these dihydroxyaromatic compounds with substantially equivalent reactivity is toprepare the bis-haloformates of each, and react the bis-haloformateswith a dihydroxy aromatic compound to form a polycarbonate structure.Bis haloformates may not react with one another directly but maysubstantially react with the dihydroxy aromatic compound, therebydisposing at least one dihydroxy aromatic compound between any two bishaloformates, and forming carbonate linkage on at least one end of thedihydroxy aromatic compound. A spacer unit may thus form by thisreaction wherein a carbonate linkage is formed one each end of adihydroxy aromatic compound. By forming the carbonate linkages in thisway, a substantially random distribution of polysiloxane units may beachieved within the polymer chain.

Suitable methods for forming copolymer compositions comprising randomlydispersed, substantially separated soft block moieties are disclosed.For example, dihydroxy compounds comprising arylate polyester units,dihydroxy compounds comprising soft block moieties, and optionallydihydroxy aromatic compounds such as a bisphenol of Formula VIII, areeach individually reacted with a carbonyl halide at a pH of 3 to 8 toform the respective bis haloformates. The bis haloformates are reactedwith a dihydroxy compound and an interfacial polymerization catalyst toform the copolymer composition at a pH of 9 to 13. In an embodiment,wherein the arylate polyester unit has one or more acyl end groups, theacyl end groups may substantially form the corresponding acid halidesupon treatment with a carbonyl halide at a pH of 3 to 8. The arylatepolyester unit may be substantially present as a bis haloformate, a bisacyl halide, a mono acyl halide/mono haloformate, a bis acylhaloformate, a mono acyl haloformate/mono acyl halide, a mono acylhaloformate/mono haloformate, a combination of two or more of these, andthe like. For the purpose of the discussion below and as used herein,the term “bis haloformate” may comprise each of these substantiallyfunctionally equivalent bis acid halides.

A Suitable method for preparing copolymer compositions comprisingrandomly dispersed polysiloxanes uses bis haloformates as a reactivecomponent. For example, in one method, the bis haloformates of each ofan arylate polyester unit, a dihydroxy compound comprising a soft blockmoiety, and optionally a dihydroxy compound of Formula VIII are formedin situ in a reaction medium further comprising a carbonyl halide,specifically phosgene, and the reaction medium is at a pH of 3 to 8. Ina specific example, wherein the soft block moiety comprises a dihydroxycompound of Formula XII, a bis-haloformate of Formula XXIV (where X is—COCl, and Y is —Cl) is substantially formed:

It is believed that the reactivity of a bis-haloformate of Formula XXIV(where X is COCl, and Y is Cl), toward a dihydroxy compound, iscomparable to that of a bis-haloformate formed of a dihydroxy compoundcomprising an arylate polyester unit, and is also comparable to thereactivity of a bis haloformate of a dihydroxy compound of Formula VIII.However, it will also be appreciated that a minimal amount of themonohaloformate (Formula XXIV, where X is H and Y is Cl) may be formedduring the bis haloformate reaction, and a smaller amount of thedihydroxy compound of Formula XII may also remain as an unreactedportion. It will be further appreciated that the presence of these maylead to the formation of undesired single carbonate linkages betweensoft block moieties during subsequent formation of a copolymercomposition.

In another embodiment, one or more dihydroxy compounds may beindividually reacted with a carbonyl source to substantially form theindividual bis-haloformates. For example, one method of substantiallyforming the bis-haloformate of a dihydroxy compound comprising apolysiloxane unit is described in U.S. Pat. No. 6,728,364 to Silva etal, incorporated herein by reference. This method involves passing thedihydroxy compound and a carbonyl halide, specifically phosgene, and acatalyst such as sodium hydroxide in aqueous solution, simultaneouslythrough a heated tube reactor to form the bis haloformate of thedihydroxy compound in a continuous process. An advantage to this processis that the bis haloformates are formed in high yield, minimizing theformation of mono-halofornate intermediates which may lead toundesirable single carbonate linkages between polysiloxane units. In aspecific embodiment, a soft block moiety comprising the dihydroxycompound of Formula XII is reacted, under the above conditions, withphosgene to form bis-haloformate of Formula XXIV (X is —COCl, Y is —Cl).

In one embodiment, the bis haloformate of a dihydroxy compoundcomprising a polysiloxane unit is combined with a bis haloformatecomprising an arylene polyester unit, and the combined bis haloformatesare reacted with a dihydroxy compound to form a copolymer composition.For example, the reacting may be conducted using a catalyst and at a pHof 9 to 13, more specifically 10 to 12. Alternatively, the bishaloformate of a dihydroxy compound of Formula VIII is present duringthe reacting of the bis haloformates with a dihydroxy compound to form acopolymer composition. In another alternative, a monohaloformate of adihydroxy compound of Formula VIII is present during the reacting of thebis haloformates with a dihydroxy compound to form a copolymercomposition. In yet another alternative, the bis haloformates arecombined with a dihydroxy compound and a carbonyl halide to form acopolymer composition.

In a specific embodiment, suitable methods for forming a copolymercomposition comprising a polysiloxane unit are disclosed. In one method,for example, a dihydroxy aromatic compound, a chain stopper, a catalyst,a dicarboxylic acid dihalide, and solvent are combined in a medium,wherein the pH of the medium is maintained at 8 or less while combiningand is biphasic, having a solvent phase and an aqueous phase. The pH isthen adjusted to 7, and a polysiloxane unit comprising one or more ofFormulas XIX or XXII is added to the medium, followed by addition ofphosgene, wherein the pH of the medium is maintained at a pH of 8 orless. The pH is adjusted to about 7, a dihydroxy aromatic compound isadded, the pH is raised to about 9 to 10, a catalyst is added, and thepH is raised to a final 9 to 12. The resulting copolymer composition maybe isolated by precipitation from the medium by addition to anon-solvent.

In another method for example, a dihydroxy aromatic compound, a chainstopper, a catalyst, a dicarboxylic acid dihalide, and solvent arecombined in a medium, wherein the pH of the medium is maintained at 8 orless and is biphasic, having a solvent phase and an aqueous phase. ThepH is adusted to about 7, the phases are separated and the solvent phaseis combined with a polysiloxane unit comprising one or more of FormulasXIX or XXII, a first dihydroxy aromatic compound, and phosgene, and thepH of the medium is maintained at a pH of 8 or less. The pH is adjustedto about 7, a second dihydroxy aromatic compound is added, the pH israised to 9 to 10, a catalyst is added, and the pH is raised to 9 to 12.The polymer may be isolated by precipitation from the reaction mediuminto a non-solvent.

In another method, a dihydroxy aromatic compound, a catalyst, and asolvent are added to a medium and adjusted to pH of 7 wherein the mediumis biphasic, having a solvent phase and an aqueous phase. A dicarboxylicacid dihalide in a solvent is added while maintaining a pH of 4 to 7.The pH of the medium is adjusted to about 7.4, and a dihydroxy aromaticcompound, a chain stopper, a catalyst, and a first portion of phosgenewhile maintaining a pH of about 9. The pH is raised to about 10, and abis haloformate of Formula XXIV (where x is COCl and y is Cl) is addedto the medium, followed by addition of a second portion of phosgene,wherein the pH of the medium is maintained at a pH of about 10. Thesolvent phase is separated from the aqueous phase and is washed with anaqueous acidic solution. A copolymer composition is isolated byprecipitation from the solvent phase by addition of a non-solvent.

In another method, for example, a dihydroxy aromatic compound, acatalyst, and a solvent are added to a medium and adjusted to pH of 7,wherein the medium is biphasic, having a solvent phase and an aqueousphase. A dicarboxylic acid dihalide in a solvent is added whilemaintaining a pH of 4 to 7. The pH of the medium is adjusted to about 8to 9, and a first portion of dihydroxy aromatic compound and a firstportion of phosgene is added while maintaining a pH of 5 to 7. The pH ofthe medium is increased to about 10 to 10.5, a polysiloxane unitcomprising one or more of Formulas XIX or XXII is added to the medium,and second portion of dihydroxy aromatic compound is added. The presenceof chloroformates is monitored, and upon their disappearance, a secondportion of phosgene is added, wherein the pH of the medium is maintainedat about 10. The solvent phase is separated from the aqueous phase andis washed with an aqueous acidic solution. A copolymer composition isisolated by precipitation from the solvent phase by addition of anon-solvent.

In another method, for example, a dicarboxylic acid dihalide, apolysiloxane unit comprising one or more of Formulas XIX or XXII, asolvent, and a catalyst are combined with a dihydroxy aromatic compoundin a medium, wherein the medium is biphasic, having a solvent phase andan aqueous phase, and the pH is adjusted to 6 to 7. A dihydroxy aromaticcompound, a chain stopper, and a catalyst is added. The pH of the mediumis maintained at about 9, and a first portion of phosgene is added. ThepH is raised to and maintained at about 10, and second portion ofphosgene is added. The solvent phase is separated from the aqueous phaseand is washed with an aqueous acidic solution. A copolymer compositionis isolated by precipitation from the solvent phase by addition of anon-solvent.

Adjustments to the pH may be made using an aqueous solution of a base,for example, 50% aqueous sodium hydroxide or caustic soda. The biphasicsolvent medium may comprise water and a substantially non-water misciblesolvent, for example, methylene chloride or toluene.

In a comparative example of a method detailed in Experiment 1 of U.S.Pat. No. 5,932,677, a copolymer is prepared by simultaneous phosgenationof a mixture of dihydroxy compounds in biphasic medium at pH 9 to 12. Inthis method, no effort is made to provide for a uniform reactivitybetween the dihydroxy aromatic compounds comprising an arylate polyesterunit, an aromatic carbonate unit, and a polysiloxane unit under theconditions of the reaction. The resulting copolymer composition appearsopaque when formed into a molded film of 25 micrometer thickness.

The introduction of a polysiloxane units comprising a structure ofFormula XIX, specifically a structure of either of Formulas XII or XVI,as a carbonate into a copolymer composition comprising a resorcinolarylate polyester unit, an aromatic carbonate unit, and a polysiloxaneunit, can result in dramatic increases in optical transmission, lowtemperature notched Izod impact strength, and weatherability, where thepolysiloxane soft-block moieties are separated by at least one spacerunit having a structure of one or more of Formulas II, III, IV, V, VII,and VIII. In another embodiment, a copolymer composition comprising abisphenol arylate polyester unit, an aromatic carbonate unit, and apolysiloxane unit, where the polysiloxane units are separated by atleast one spacer unit having a structure of one or more of Formulas II,III, IV, V, VII, and VIII has high optical transmission, and excellentmelt flow and ductility properties.

In one embodiment, the composition (or articles prepared therefrom) mayexhibit one or more of the following desirable properties: a percenttransmission of at least 55%, specifically at least 60%, and morespecifically at least 70%, measured according to ASTM D1003-00 at asample thickness of 3.2 millimeters; a percent haze of less than orequal to 30%, specifically less than or equal to 25%, and morespecifically less than or equal to 20%, as measured according to ASTMD1003-00 at a sample thickness of 3.2 millimeters; a melt volume ratio(MVR) of 1 to 45, more specifically 2 to 30 cm³/10 minutes, measured at300° C./1.2 kg in accordance with ASTM D1238-04.

The poly(resorcinol arylate polysiloxane polycarbonate) may further havea heat deformation temperature (HDT) of 100 to 170° C., morespecifically 110 to 160° C., measured at 66 psi according to ISO 179.The poly(resorcinol arylate polysiloxane polycarbonate) may have anotched Izod impact strength of 4.3 to 8 Joules per centimeter (J/cm),more specifically 4.8 to 7.5 J/cm, measured according to ASTM D256-04 at23° C.; a notched Izod impact strength of 2.7 to 8 Joules per centimeter(J/cm), more specifically at least 3.7 to 6.4 J/cm, measured accordingto ASTM D256-04 at −20° C.; and a notched Izod impact strength of 1.6 to5.3 Joules per centimeter (J/cm), more specifically at least 2.1 to 4.3J/cm, measured according to ASTM D256-04 at −40° C. The poly(resorcinolarylate polysiloxane polycarbonate) may be 80 to 100% ductile attemperatures up to −40° C. The compositions may further have %elongation of 30 to 120%, or 60 to 115%, measured in accordance withASTM 256-04.

Shaped, formed, or molded articles comprising the copolymer compositionsare also provided. The copolymer compositions may be molded into usefulshaped articles by a variety of means such as injection molding,extrusion, rotational molding, blow molding and thermoforming to formarticles such as, for example, computer and business machine housingssuch as housings for monitors, handheld electronic device housings suchas housings for cell phones, electrical connectors, medical devices,membrane devices, and components of lighting fixtures, ornaments, homeappliances, roofs, greenhouses, sun rooms, swimming pool enclosures, andthe like.

Other representative weatherable articles that may be fabricated usingthe copolymer compositions provided herein include aircraft, automotive,truck, military vehicle (including automotive, aircraft, and water-bornevehicles), and motorcycle exterior and interior components, includingpanels, quarter panels, rocker panels, trim, fenders, doors, decklids,trunklids, hoods, bonnets, roofs, bumpers, fascia, grilles, mirrorhousings, pillar appliques, cladding, body side moldings, wheel covers,hubcaps, door handles, spoilers, window frames, headlamp bezels,headlamps, tail lamps, tail lamp housings, tail lamp bezels, licenseplate enclosures, roof racks, and running boards; enclosures, housings,panels, and parts for outdoor vehicles and device; enclosures forelectrical and telecommunication devices: outdoor furniture; boats andmarine equipment, including trim, enclosures, and housings; outboardmotor housings; depth finder housings, personal water-craft; jet-skis;pools; spas; hot-tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, windows, floors, decorative windowfurnishings or treatments; treated glass covers for pictures, paintings,posters, and like display items; optical lenses; ophthalmic lenses;corrective ophthalmic lenses; implantable ophthalmic lenses; wallpanels, and doors; protected graphics; outdoor and indoor signs;enclosures, housings, panels, and parts for automatic teller machines(ATM); enclosures, housings, panels, and parts for lawn and gardentractors, lawn mowers, and tools, including lawn and garden tools;window and door trim; sports equipment and toys; enclosures, housings,panels, and parts for snowmobiles; recreational vehicle panels andcomponents; playground equipment; articles made from plastic-woodcombinations; golf course markers; utility pit covers; computerhousings; desk-top computer housings; portable computer housings;lap-top computer housings; palm-held computer housings; monitorhousings; printer housings; keyboards; FAX machine housings; copierhousings; telephone housings; mobile phone housings; radio senderhousings; radio receiver housings; light fixtures; lighting appliances;network interface device housings; transformer housings; air conditionerhousings; cladding or seating for public transportation; cladding orseating for trains, subways, or buses; meter housings; antenna housings;cladding for satellite dishes; (coated helmets and personal protectiveequipment; coated synthetic or natural textiles; coated photographicfilm and photographic prints; coated painted articles; coated dyedarticles; coated fluorescent articles; coated foam articles; and likeapplications. Additional fabrication operations may be performed onarticles, such as, but not limited to molding, in-mold decoration,baking in a paint oven, lamination, and/or thermoforming.

EXAMPLES

The invention is illustrated by the following, non-limiting examples.All parts are by weight unless otherwise designated. GPC data wasacquired using an Agilent 1100 Series chromatograph equipped with a UVdetector using chloroform as the mobile phase and polystyrene asmolecular weight standards. Alternatively, another GPC (Waters Inc. UVdetection system) with 100% methylene chloride (toluene flow marker) wasused at 1.5 mL per minute on two Polymer Labs Mixed C size exclusioncolumns connected in series and held at 32° C., calibrated usingpolycarbonate standards, and analyzed by Waters. Inc. Milleniumsoftware. Glass transition temperature (Tg) was determined usingdifferential scanning calorimetry at a scan rate of 10° C./minute.

The compositions are tested for the following properties: Transmittance(also referred to as “transmission”) (%) was determined according toASTM D1003-00 using a Gardner Haze Guard Dual, on 3.2 or 1.6 millimeterthick molded plaques. Izod Notched Impact strength and % ductility weremeasured according to ISO 180-1A on 4 and 3.12 millimeter thick testbars and at various temperatures (see ASTM D256-04 for NI testing at 23°C.).

Methods for preparation of polymers of the present disclosure areprovided as Examples 6–18, below. For each of the general proceduresdescribed as Examples 6–18, reactions were performed using apolycondensation reactor comprising either of a two-liter, five neckMorton flask equipped with mechanical stirrer, reflux condenser, pHprobe, acid chloride solution inlet and base solution inlet, or asimilarly outfitted five-liter flask. Additionally, two peristalticpumps were used for metered delivery of acid chloride and basesolutions, respectively. Alternatively, the acid chloride was meteredinto the reaction flask using a graduated addition funnel.

Example 6

Procedure 1 for the preparation of poly(resorcinol arylate polysiloxanepolycarbonate). The following were added to a two-liter five-neckedglass reactor: resorcinol (35.25 g, 0.32 mol); deionized water (50–70ml); anhydrous methylene chloride, HPLC grade (450 ml); para-cumylphenol (1.74 g, 0.008 mol); and methyltributylammonium chloride (0.3 mlof a 75 weight percent solution in water). A solution of a 50:50 mixtureof iso:terepthaloyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was then added over a period of10–20 minutes while the pH of the reaction was maintained at 4 to 8 withthe addition of 50 wt % sodium hydroxide solution in water. Afteraddition of the diacid chloride, the pH of the reaction was adjusted to7. The polyarylate mixture was charged with a polysiloxane of FormulaXII (5.96 g, 0.002 mol); deionized water (200 ml), and phosgene (9.7 g,1.0 g/min., 0.10 mol) while the pH was maintained at 4 to 8 by theaddition of a 50 wt % sodium hydroxide solution in water. After thecomplete addition of phosgene, the reaction medium was brought to a pHof 7 by the addition of sodium hydroxide solution. The contents of thereactor were checked for the presence of chloroformate molecules withphosgene paper. To the bis-chloroformate solution was added bisphenol-A(14.04 g, 0.06 mol) and methylene chloride (200 ml), and the pH wasraised to 9 to 10. The reaction was stirred for 10–15 minutes.Triethylamine (1.3 g) was added, the pH was adjusted to 9 to 12, and thecontents were stirred until all of the chloroformate molecules weredetermined to be not present by analysis of the reaction components. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Example 7

Procedure 2 for the preparation of poly(resorcinol arylate polysiloxanepolycarbonate). The following were added to a two-liter five-neckedround bottom polycondensation reactor: resorcinol (29.83 g, 0.27 mol);deionized water (50–70 ml); anhydrous methylene chloride, HPLC grade(450 ml); para-cumyl phenol (1.74 g, 0.008 mol); andmethyltributylammonium chloride (0.3 ml of a 75 weight percent solutionin water). A solution of a 50:50 mixture of iso:terepthaloyl chloridedissolved in anhydrous methylene chloride (150.1 g, 0.25 mol of diacidchloride) was then added over a period of 10–20 minutes while the pH ofthe reaction was maintained at 4 to 8 with the addition of 50% by wt.sodium hydroxide solution in water. After the complete addition of thediacid chloride, the pH of the reaction was adjusted to 7, and theorganic layer containing the polyarylate was extracted from the aqueouslayer. The aqueous layer was discarded, and the organic-soluble contentswere transferred back into the two-liter five-necked glass reactor. Thepolyarylate mixture was charged with polysiloxane of Formula XII (5.16g, 0.0016 mol); BPA (3.09 g, 0.013 mol); deionized water (400 ml), andphosgene (5.1 g, 1.0 g/min., 0.05 mol) while the pH was maintained at 4to 8 by the addition of a 50% by wt. sodium hydroxide solution in water.After the complete addition of phosgene, the reaction medium was broughtto a pH of 7 by the addition of sodium hydroxide solution. The contentsof the reactor were checked for the presence of chloroformate moleculeswith phosgene paper. To the bis-chloroformate solution was added asecond charge of BPA (3.09 g, 0.013 mol) and methylene chloride (200ml), and the pH was raised to 10. The reaction was stirred for 10–15minutes. Triethylamine (1.15 g) was added and the contents were stirreduntil all of the chloroformate molecules were judged to be absent by ananalytical method. The poly(resorcinol arylate polysiloxanepolycarbonate) was purified and dried by the conventional methods usedin the production of polycarbonate.

Example 8

Example 7 was repeated with the following reaction conditions:resorcinol (35.25 g, 0.32 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (1.74 g,0.008 mol) and methyltributylammonium chloride (0.3 ml of a 75 weightpercent solution in water). A solution of a 50:50 mixture ofiso:terepthaloyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was added to the reactor over aperiod of 10–15 minutes via an addition funnel. After the polyestercondensation, the polyarylate mixture was charged with polysiloxane ofFormula XII (2.74 g, 0.0008 mol); deionized water (400 ml), and phosgene(9.6 g, 1.0 g/min., 0.10 mol). To the bis-chloroformate solution wasadded BPA (6.23 g, 0.027 mol) and methylene chloride (200 ml), and thepH was raised to 10. The reaction was stirred for 10–15 minutes.Triethylamine (1.15 g) was added and the contents were stirred until allof the chloroformate molecules were judged to be absent by an analyticalmethod. The poly(resorcinol arylate polysiloxane polycarbonate) waspurified and dried by the conventional methods used in the production ofpolycarbonate.

Example 9

Example 7 was repeated with the following reaction conditions:resorcinol (29.83 g, 0.27 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml) para-cumyl phenol (1.96 g, 0.009mol) and methyltributylammonium chloride (0.3 ml of a 75 weight percentsolution in water). A solution of a 50:50 mixture of iso:terepthalylchloride dissolved in anhydrous methylene chloride (150.1 g, 0.25 mol ofdiacid chloride) After the polyester condensation, the polyarylatemixture was charged with a polysiloxane of Formula XII (2.81 g, 0.0009mol); BPA (7.02 g, 0.031 mol) deionized water (400 ml), and phosgene(7.4 g, 1.0 g/min., 0.07 mol). To the bis-chloroformate solution wasadded a second charge of BPA (7.02 g, 0.031 mol) and methylene chloride(200 ml), and the pH was raised to 10. The reaction was stirred for10–15 minutes. Triethylamine (1.29 g) was added and the contents werestirred until all of the chloroformate molecules had condensed. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Example 10

Example 7 was repeated with the following reaction conditions:resorcinol (29.83 g, 0.27 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (1.75 g,0.008 mol) and methyltributylammonium chloride (0.3 ml of a 75 weightpercent solution in water). A solution of a 50:50 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was charged into the flask via anaddition funnel. After the polyester condensation, the polyarylatemixture was charged with a polysiloxane of Formula XII (5.16 g, 0.0016mol); BPA (3.11 g, 0.014 mol); deionized water (400 ml), and phosgene(5.3 g, 1.0 g/min., 0.05 mol). To the bis-chloroformate solution wasadded a second charge of BPA (3.11 g, 0.014 mol) and methylene chloride(200 ml), and the pH was raised to 10. The reaction was stirred for10–15 minutes. Triethylamine (1.16 g) was added and the contents werestirred until all of the chloroformate molecules had condensed. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Example 11

Example 7 was repeated with the following reaction conditions:resorcinol (35.25 g, 0.32 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (1.96 g,0.009 mol) and methyltributylammonium chloride (0.3 ml of a 75 weightpercent solution in water). A solution of a 50:50 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was added over a period of 10–15minutes. After the polyester condensation, the polyarylate mixture wascharged with a polysiloxane of Formula XII (2.81 g, 0.0009 mol); BPA(7.02 g, 0.031 mol) deionized water (400 ml), and phosgene (13.7 g, 1.0g/min., 0.139 mol). To the bis-chloroformate solution was added a secondcharge of BPA (7.02 g, 0.031 mol) and methylene chloride (200 ml), andthe pH was raised to 10. The reaction was stirred for 10–15 minutes.Triethylamine (1.30 g) was added and the contents were stirred until allof the chloroformate molecules had condensed. The poly(resorcinolarylate polysiloxane polycarbonate) was purified and dried by theconventional methods used in the production of polycarbonate.

Example 12

Example 6 was repeated with the following reaction conditions:resorcinol (35.25 g, 0.32 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (2.29 g,0.011 mol) and methyltributylammonium chloride (0.3 ml of a 75 weigthpercent solution in water). A solution of a 50:50 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride). After the polyestercondensation, the polyarylate mixture was charged with a polysiloxane ofFormula XII (2.98 g, 0.0009 mol); BPA (7.02 g, 0.031 mol); deionizedwater (400 ml), and phosgene (9.6 g, 1.0 g/min., 0.10 mol). To thebis-chloroformate solution was added a second charge of BPA (7.02 g,0.031 mol) and methylene chloride (200 ml), and the pH was raised to 10.The reaction was stirred for 10–15 minutes. Triethylamine (1.30 g) wasadded and the contents were stirred until all of the chloroformatemolecules were absent by an analytical determination. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Example 13

Example 6 was repeated with the following reaction conditions:resorcinol (35.25 g, 0.32 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (1.75 g,0.008 mol) and methyltributylammonium chloride (0.3 ml of a 75 weightpercent solution in water). A solution of a 50:50 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was added to the reactor over aperiod of 10–15 minutes via an addition funnel. After the polyestercondensation, the polyarylate mixture was charged with a polysiloxane ofFormula XII (5.49 g, 0.0017 mol); BPA (3.09 g 0.0135 mol); deionizedwater (400 ml), and phosgene (11.44 g, 1.0 g/min., 0.116 mol). To thebis-chloroformate solution was added a second charge of BPA (3.09 g0.0135 mol) and methylene chloride (200 ml), and the pH was raised to10. The reaction was stirred for 10–15 minutes. Triethylamine (1.16 g)was added and the contents were stirred until all of the chloroformatemolecules were judged to be absent by an analytical method. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Example 14

Example 6 was repeated with the following reaction conditions:resorcinol (29.83 g, 0.27 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (2.62 g,0.012 mol) and methyltributylammonium chloride (0.3 ml of a 75 weightpercent solution in water). A solution of a 50:50 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was added to the reactor over aperiod of 10–15 minutes via an addition funnel. After the polyestercondensation, the polyarylate mixture was charged with a polysiloxane ofFormula XII (7.03 g, 0.0021 mol); BPA (18.7 g 0.082 mol); deionizedwater (400 ml), and phosgene (13.98 g, 1.0 g/min., 0.141 mol). To thebis-chloroformate solution was added a second charge of BPA (18.7 g0.082 mol) and methylene chloride (200 ml), and the pH was raised to 10.The reaction was stirred for 10–15 minutes. Triethylamine (1.74 g) wasadded and the contents were stirred until all of the chloroformatemolecules were judged to be absent by an analytical method. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Example 15

Example 7 was repeated with the following reaction conditions:resorcinol (35.25 g, 0.32 mol); deionized water (50–70 ml); anhydrousmethylene chloride, HPLC grade (450 ml); para-cumyl phenol (2.62 g,0.012 mol) and methyltributylammonium chloride (0.3 ml of a 75 weightpercent solution in water). A solution of a 50:50 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride(150.1 g, 0.25 mol of diacid chloride) was added to the reactor over aperiod of 10–15 minutes via an addition funnel. After the polyestercondensation, the polyarylate mixture was charged with a polysiloxane ofFormula XII (7.03 g, 0.0021 mol); BPA (18.7 g 0.082 mol); deionizedwater (400 ml), and phosgene (20.31 g, 1.0 g/min., 0.205 mol). To thebis-chloroformate solution was added a second charge of BPA (18.7 g0.082 mol) and methylene chloride (200 ml), and the pH was raised to 10.The reaction was stirred for 10–15 minutes. Triethylamine (1.74 g) wasadded and the contents were stirred until all of the chloroformatemolecules were judged to be absent by an analytical method. Thepoly(resorcinol arylate polysiloxane polycarbonate) was purified anddried by the conventional methods used in the production ofpolycarbonate.

Comparative Example 1

The following components were charged into a five-liter Morton roundbottom flask: resorcinol (29.83 g, 0.27 mol); (b) deionized water (50 to70 ml); (c) methylene chloride (450 ml) (d) para-cumyl phenol (2.62 g,0.012 mol). A solution of a 50:50 mixture of iso:terepthalyl chloridedissolved in anhydrous methylene chloride (150.1 g, 0.25 mol of diacidchloride) was added to the flask. After the polyester condensation, thepolyarylate mixture was charged with a polysiloxane of Formula XII (7.03g, 0.0021 mol); (b) BPA (18.7 g, 0.082 mol); (c) deionized water (400ml), and (d) phosgene (13.98 g, 1.0 g/min., 0.141 mol), and (e)triethylamine (1.74 g). The reaction was stirred for the requiredreaction time and until all of the chloroformate molecules were judgedto be absent by an analytical method. The poly(resorcinol arylatepolysiloxane polycarbonate) was purified and dried by the conventionalmethods used in the production of polycarbonate.

Comparative Example 2

Experiment 1 of U.S. Pat. No. 5,932,677 was repeated on a smaller scale,similar to Examples 1–10 and Comparative Example 1. The followingcomponents were charged into a five-liter Morton round bottom flasksimilar to the reactor described in Ex. 1: deionized water (50 to 70ml); (b) methylene chloride(450 ml) (c) para-cumyl phenol (1.61 g,0.0065 mol), (d) BPA (26.95 g, 0.118 mol), (e) XII (1.41 g, 0.0004 mol),and (f) triethylamine (0.91 g). A solution of a 93:7 mixture ofiso:terepthalyl chloride dissolved in anhydrous methylene chloride (20g, 0.0985 mol of diacid chloride) was added to the flask. During thepolyester condensation, reaction the pH of the reaction was maintainedat 8 to 10. After the addition of the diacid chloride, the reactor wascharged with phosgene (2.58 g, 0.026 mol). The reaction was stirred forthe required reaction time and until all of the chloroformate moleculeswere judged to be absent by an analytical method. The poly(resorcinolarylate polysiloxane polycarbonate) was purified and dried by theconventional methods used in the production of polycarbonate.

Properties of the poly(resorcinol arylate polysiloxane polycarbonate)sprepared according to the above methods are tabulated in Table I, below,wherein Mw is molecular weight, Tg is the glass transition temperature,film appearance is a qualitative visual assessment, and % T is thepercent transmittance.

TABLE I Mw Ig Sample wt. % XII (g/mol) (° C.) Film appearance % TExample 6 6 23,300 130.6 transparent 91.1^(a) Example 7 6 28,900 146.5transparent 90.8^(a) Example 8 3 25,700 146.6 transparent 88.4^(a)Example 9 6 28,700 145.3 transparent 90.6^(a) Example 10 6 30,000 148.9transparent 87.5^(a) Example 11 3 25,000 142.7 transparent 92.3^(a)Example 12 3 25,800 135.3 transparent 90.3^(a) Example 13 6 30,400 135.7transparent 92^(a) Example 14 6 31,600 146.2 transparent 90.7^(a)Example 15 6 15,600 131.4 transparent 91.7^(a) Comp. Ex. 1 6 25,700 140opaque^(c) 34.2^(a) Comp. Ex. 2 3 27,100 176 opaque^(c) 33.1 ^(a)Filmswere melt-pressed at 205° C. and 13.8 megapascals to 10–30 micrometerthickness. ^(b)Parts were injection molded color plaques with 3.2 mmthickness. ^(c)% haze > 99%.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety. All ranges disclosedherein are inclusive of the endpoints, and endpoints directed to thesame characteristic are independently combinable with each other.

While the invention has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present invention. As such,further modifications and equivalents of the invention herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the spirit and scope of the invention as defined by thefollowing claims. All U.S. Patents cited herein are incorporated hereinby reference.

1. A copolymer composition comprising an arylate polyester unit; anaromatic carbonate unit; and a soft-block moiety; wherein individualoccurrences of the soft block moiety are substantially linked to eachother by a spacer unit comprising one or more of the arylate polyesterunits, one or more of the aromatic carbonate units, or a combinationcomprising each of these.
 2. The copolymer composition of claim 1,wherein occurrences of the soft block moiety are substantially randomlydispersed within a polymer chain.
 3. The copolymer composition of claim2, wherein the soft block moiety is a polysiloxane unit.
 4. Thecopolymer composition of claim 1 wherein the arylate polyester unitcomprises the Formula

wherein D¹ is the reaction residue of a dihydroxy aromatic compound. 5.The copolymer composition of claim 4, wherein the dihydroxy aromaticcompound has the Formula

wherein it is 0–3, and R^(y) is selected from the group consisting ofC₁₋₁₂ alkyl, halogen, and a combination comprising one or more of these.6. The copolymer composition of claim 4, wherein the dihydroxy aromaticcompound has the Formula

wherein each of R³–R¹⁰ is independently selected from the groupconsisting of hydrogen, halogen, nitro, cyano, C₁–C₃₀ alkyl, C₄–C₃₀cycloalkyl, C₆–C₃₀ aryl, C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy, and C₆–C₃₀aryloxy; an W is a connecting unit selected from the group consisting ofa direct bond, oxygen atom, sulfur atom, C═O, SO₂, C₁–C₂₀ aliphaticradical, C₆–C₂₀ aromatic radical, and a C₆–C₂₀ cycloaliphatic radical.7. The copolymer composition of claim 4 wherein the arylate polyesterunits comprise the diradical of isophthalic acid, terephthalic acid, ora combination of isophthalic acid and terephthalic acid.
 8. Thecopolymer composition of claim 7 wherein arylate polyester unitscomprise the diradicals of a combination of isophthalic acid; andterephthalic acid and wherein the molar ratio of isophthalic acid toterephthalic acid is 1:99 to 99:1.
 9. The copolymer composition of claim1 wherein the aromatic carbonate unit comprises at least about 60 mol-%of the reaction residue of dihydroxy aromatic compounds of Formula

wherein each of R³–R¹⁰ is independently selected from the groupconsisting of hydrogen, halogen, nitro, cyano, C₁–C₃₀ alkyl, C₄–C₃₀cycloalkyl, C₆–C₃₀ aryl, C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy, and C₆–C₃₀aryloxy, and W is a connecting unit selected from the group consistingof a direct bond, oxygen atom, sulfur atom, C═O, SO₂, C₁–C₂₀ aliphaticradical, C₆–C₂₀ aromatic radical, and a C₆–C₂₀ cycloaliphatic radical.10. The copolymer composition of claim 3 wherein the polysiloxane unitcomprises repeating diorganosiloxane units of Formula

wherein each occurrence of R³ is independently C₁–C₁₂ hydrocarbyl. 11.The copolymer composition of claim 10 wherein the polysiloxane unit hasthe Formula

wherein x is 1 to 1000, wherein each R³ is independently a C₁–C₁₂hydrocarbyl, each occurrence of R⁴ is independently a divalent C₁–C₃₀hydrocarbylene, and each polysiloxane unit is the reaction residue ofits corresponding dihydroxy compound.
 12. The copolymer composition ofclaim 11, wherein each occurrence of R⁴ is independently of Formula:

wherein each occurrence of R⁵ is independently halogen, cyano, nitro,C₁–C₈ alkylthio, C₁–C₈ alkyl, C₁–C₈ alkoxy, C₂–C₈ alkenyl, C₂–C₈alkenyloxy group, C₃–C₈ cycloalkyl, C₃–C₈ cycloalkoxy, C₆–C₁₀ aryl,C₆–C₁₀ aryloxy, C₇–C₁₂ aralkyl, C₇–C₁₂ aralkoxy, C₇–C₁₂ alkaryl, orC₇–C₁₂ alkaryloxy; each occurrence of R⁶ is independently H or C₁–C₁₂hydrocarbyl; b is 1 to 8; and each a is independently 0, 1, 2, 3, or 4.13. The copolymer composition of claim 12 wherein the polysiloxane unitsare each individually reaction residues of the Formula

wherein q is 1 to
 99. 14. The copolymer composition of claim 10 whereinthe polysiloxane unit has the Formula

wherein x is 1 to 1000 and D¹ is the reaction residue of a dihydroxyaromatic compound.
 15. The copolymer composition of claim 14 wherein thepolysiloxane units are each individually reaction residue of the Formula

wherein x is 10 to 100, and Ar represents the reaction residue of adihydroxy aromatic compound.
 16. The copolymer composition of claim 10comprising 0.1 to 75 weight percent of polysiloxane units.
 17. Thecopolymer composition of claim 1 further comprising a chain stopper. 18.The copolymer composition of claim 1 wherein a film comprising thecopolymer composition has an optical transmittance of greater than orequal to 60%, as measured according to ASTM D1003-00.
 19. A method offorming a copolymer composition comprising substantially forming thebis-haloformates of a dihydroxy compound comprising an arylate polyesterunit; and a dihydroxy compound comprising a soft-block moiety; andreacting the bis haloformates with a dihydroxy aromatic compound. 20.The method of claim 19 further comprising reacting a haloformate of adihydroxy aromatic compound with the bis haloformates and thedihydroxyaromatic compound.
 21. The method of claim 20 wherein thehaloformate of the dihydroxy aromatic compound is substantially eitherone of the monohaloformate or the bis haloformate of the dihydroxyaromatic compound.
 22. The method of claim 19 further comprising a chainstopper.
 23. The method of claim 19 further comprising reacting the bishaloformates and the dihydroxy aromatic compound with a carbonylatingagent.
 24. The method of claim 19 where the reacting is carried out at apH of 9 to
 12. 25. The method of claim 19 wherein the arylate polyesterunit comprises the Formula

wherein D¹ is the reaction residue of a dihydroxy aromatic compound. 26.The method of claim 19 wherein the arylate polyester unit of thecopolymer composition comprises the diradicals of a combination ofisophthalic acid and terephthalic acid; and wherein the molar ratio ofisophthalic acid to terephthalic acid is 1:99 to 99:1.
 27. The method ofclaim 19 wherein the aromatic carbonate comprises at least about 60mol-% of the reaction residue of a dihydroxy aromatic compound ofFormula

wherein each of R³–R¹⁰ is independently selected from the groupconsisting of hydrogen, halogen, nitro, cyano, C₁–C₃₀ alkyl, C₄–C₃₀cycloalkyl, C₆–C₃₀ aryl, C₁–C₃₀ alkoxy, C₄–C₃₀ cycloalkoxy, and C₆–C₃₀aryloxy, and W is a connecting unit selected from the group consistingof a direct bond, oxygen atom, sulfur atom, C═O, SO₂, C₁–C₂₀ aliphaticradical, C₆–C₂₀ aromatic radical, and a C₆–C₂₀ cycloaliphatic radical.28. The method of claim 19 wherein the soft block moiety comprises thereaction residue of a polysiloxane unit having hydroxy end groups, andwherein the polysiloxane unit comprises repeating siloxane units ofFormula

wherein each occurrence of R³ is independently C₁–C₁₂ hydrocarbyl. 29.The method of claim 28 wherein the hydroxy end groups of thepolysiloxane unit are hydroxyaromatic groups having at least onesubstituent group positioned ortho to the hydroxy group.
 30. The methodof claim 19 wherein a film comprising the copolymer composition has anoptical transmittance of greater than or equal to 60% as measuredaccording to ASTM D1003-00.